POLYIMIDE CONTAINING CROSSLINKABLE GROUP AND PROCESS FOR PRODUCING THE SAME

Abstract

 This invention provides crosslinkable-group-containing polyimides of various known thermoplastic polyimide backbone structures, which are provided with far better heat resistance, chemical resistance and mechanical properties than known polyimides of the structures without impairing excellent moldability or formability, superb sliding property, low water absorption property, outstanding electrical properties, high thermal oxidation stability and high radiation resistance, all of which are inherent to the structures.

Description

Technical Field

[0001] This invention relates to crosslinkable-group-containing polyamic acids, melt-moldable or formable, crosslinkable-group-containing polyimides, production processes thereof, and crosslinked thermoplastic polyimides obtained by heat-treating them. Specifically, the present invention is concerned with crosslinked thermoplastic polyimides having various excellent properties inherent to polyimides, namely, high heat resistance, excellent mechanical properties, superb sliding property, low water absorption property, outstanding electrical properties, high thermal oxidation resistance, high chemical resistance and high radiation resistance, especially those improved more markedly in heat resistance, chemical resistance and mechanical properties, crosslinkable-group-containing polyimides which are thermoplastic and melt-moldable or formable, crosslinkable-group-containing polyamic acids as precursors of the crosslinkable-group-containing polyimides, production proceses thereof, and their solutions or suspensions.

Background Art

[0002] Polyimides have been used widely for many years as molding or otherwise forming materials, composite materials, or electrical or electronic materials in various fields, because in addition to their superb heat resistance, they are also excellent in mechanical properties and electrical properties.

[0003] For example, a polyimide ("Kapton", "Vespel", trade names; products of E.I. DuPont de Nemours & Co., Inc.) of the formula (A) is known as a representative polyimide:

This polyimide is non-thermoplastic and is insoluble and infusible, and hence has a drawback in moldability or formability. It is therefore accompanied by a problem that no mass production is practically feasible. As a specific processing method, a block is obtained using a special molding process called powder sintering molding, and then, mechanical working such as cutting, grinding and polishing is applied to the block to obtain a formed, product.

[0004] As an amorphous thermoplastic polyimide with improved moldability or formability, a polyetherimide represented by the formula (B) ("Ultem", trade name; product of General Electric Company) is known:

However, this polyimide is soluble in amide-type aprotonic polar solvents and halogenated hydrocarbon solvents and is inferior in chemical resistance. In addition, its glass transition temperature is 215°C, and a further improvement in heat resistance is desired depending on the application.

[0005] Further, a polyimide which is imparted with moldability or formability and is represented by the formula (C):

shows melt fluidity at its melting point and higher and permits melt molding or forming while retaining the inherent properties of polyimides because it has a melting point at 385°C(U.S. Patent No. 5,043,419). Although the glass transition temperature of this polyimide is relatively high, i.e., 250°C, marked reductions in properties, which are accompanied by deformation, softening or the like, take place when used at the glass transition temperature or higher. Further improvements are therefore desired depending on its application. Further, this polyimide is inferior in chemical resistance especially under stress, and an improvement is strongly desired in this respect.

[0006] Since the properties of a thermoplastic polyimide depend on the backbone structure of the polyimide, a variety of polyimides are selected in view of their inherent performance such as heat resistance, moldability or formability, mechanical properties and chemical resistance. Nonetheless, one or more of these individual properties may be found to be insufficient depending on the application, leading to an outstanding desire for the improvement of the above-described various properties.

[0007] On the other hand, a variety of thermosetting polyimides are available on the market. As a representative example of these polyimides, a polyimide available from monomers represented by the formula (D) :

is known ["Kerimid-601", trade name; product of Rhone-Poulenc SA; F.D. Darmory, "National SAMPLE Symposium", 19, 693 (1974)]. As this polyimide is thermosetting, it is less susceptible to deformation or softening than thermoplastic polyimides and therefore, can be used under high temperature condition. However, this polyimide is not high in mechanical properties, especially in toughness and is weak against external force such as an impact. Due to its thermosetting property, no melt molding or forming is feasible. It is therefore necessary to carry out shaping at the stage of a prepolymer before its hardening and then to conduct heat treatment.

[0008] For the purpose of making improvements in the detrimental mechanical properties of these thermosetting polyimides, it is known to use a linear polyimide as a backbone and then to introduce crosslinking members into its ends and/or substituent groups. Reference may be had, for example, to U.S. Patent No. 5,138,028, U.S. Patent No. 5,478,915, U.S. Patent No. 5,493,002, U.S. Patent No. 5,567,800, U.S. Patent No. 5,644,022, U.S. Patent No. 5,412,066, and U.S. Patent No. 5,606,014.

[0009] As technical details, U.S. Patent No. 5,567,800, for example, discloses thermosetting polyimides available from heat treatment of imide oligomers having carbon-carbon triple bonds at their molecule ends, which can in turn be obtained from monomers represented by the formula (E):

and an end blocking agent, respectively. Although the polyimides disclosed in this patent have various excellent properties, they still do not permit melt molding or forming, and therefore, their molding or forming is limited to processing which makes use of solutions of polyamic acids as precursors. In general, subsequent to the shaping of a solution of a polyamic acid, removal of the solvent and a dehydrating imidation reaction are conducted by heating. As this processing involves the removal of the solvent, it is generally impossible to obtain a molded or formed product having a large thickness. This processing is therefore limited in shape to films or sheets, and further, involves problems such as foaming due to remaining solvent and a need for recovery of a great deal of solvent.

Disclosure of the Invention

[0010] An object of the present invention is to provide crosslinkable-group-containing polyimides of various known thermoplastic polyimide backbone structures, which are provided with far better heat resistance, chemical resistance and mechanical properties than known polyimides of the structures without impairing advantages inherent to the structure, such as excellent moldability or formability, superb sliding property, low water absorption property, outstanding electrical properties, high thermal oxidation stability and high radiation resistance.

[0011] Specifically described, the terms "heat resistance", "chemical resistance" and "mechanical properties" the improvements of. which constitute one of themes sought for attainment by the present invention mean, for example, physical property values and test results such as those to be described below.

① Concerning heat resistance, representative examples can include glass transition temperature; softening temperature, deflection temperature under load, and mechanical properties at high temperatures in thermal mechanical analyses; retentions of mechanical properties in thermal cycle tests; solder reflow heat resistance test; heat resistance test; and hot air aging test. Among these, the themes the attainment of which are sought for in the present invention can include especially deflection temperature under load, mechanical properties at high temperatures, retentions of mechanical properties in thermal cycle tests, and the like.

② As to chemical resistance, representative examples can include solvent dissolution resistance test, solvent immersion test, under-stress solvent immersion resistance resistance test, and retentions of various physical properties after immersion in solvent under stress. Among these, the themes the attainment of which are sought for in the present invention can include especially unders-stress solvent immersion resistance test, retentions of various physical properties after immersion in solvent under stress, and the like.

③ In respect to mechanical properties, representative examples can include tensile test, compression test, bending test, Izod impact test, and fatigue test. Among these, the themes the attainment of which is sought for in the present invention can include especially yield strength, tensile modulus, flexural modulus, Izod impact value, and the like.

[0012] Describing in other words from another viewpoint, the themes the attainment, of which is sought for by the present invention are to provide a crosslinkable-group-containing polyimide imparted with thermoplasticity by additionally providing it with high moldability or formability, which has not been brought about by conventional polyimides of the end-curing type, while retaining excellent physical properties inherent to thermosetting polyimides of the end-curing type, that is, superb sliding property, low water absorption property, outstanding electrical properties, high thermal oxidation stability, high chemical resistance and excellent mechanical properties.

[0013] Accordingly, an object of the present invention is to provide a crosslinkable-group-containing polyimide, which is thermoplastic and permits melt moldability or formability, or a crosslinkable-group-containing polyamic acid which is a precursor of the polyimide. Another object of the present invention is to provide its production process.

[0014] It is an important feature of the present invention that the crosslinkable-group-containing polyimide according to the present invention permits melt molding or forming despite its inclusion of crosslinkable groups, which allow a crosslinking reaction, and the crosslinkable-group-containing thermoplastic polyimide shows thermoplasticity. It is here that the crosslinkable-group-containing polyimide according to the present invention is totally different from the conventional thermosetting resins which are crosslinkable. The present invention is based on a novel concept never in existence to date, and has made it possible to achieve mutually contradictory matters of intermolecular crosslinking and melt fluidity.

[0015] To achieve the above-described objects, the present inventors have proceeded with an extensive investigation. As a result, it has found that a crosslinkable-group-containing polyimide molecule ends of which are blocked with 1 to 80 mole % of a crosslinkable-group-containing dicarboxylic acid anhydride and 99 to 20 mole % of a crosslinkable-group-free dicarboxylic acid anhydride can achieve the above-described objects and permits melt molding or forming despite it has been more significantly improved and is outstanding especially in heat resistance, chemical resistance and mechanical properties, leading to the completion of the present invention.

[0016] Described specifically, the present invention provides the following polyimides or processes (1)- (35) :

(1) A crosslinkable-group-containing polyimide comprising crosslinkable groups at 1 to 80 mole % of molecule ends thereof.

(2) A crosslinkable-group-containing polyimide as described in claim 1, wherein a backbone structure which forms the polyimide is substantially provided with thermoplasticity.

(3) A crosslinkable-group-containing polyimide as described above under (1) or (2), said polyimide permitting melt molding or forming, wherein 1 to 80 mole % of the molecule ends are crosslinkable-group-containing molecule ends represented by the chemical formula (2a) and 99 to 20 mole % of the molecule ends are crosslinking-group-free molecule ends represented by the chemical formula (2b):

   wherein Y represents a trivalent aromatic group selected from the group consisting:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group; and

wherein T represents a divalent aromatic group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulf one group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

(4) A crosslinkable-group-containing polyimide as described above under any one of (1)-(3), wherein the polyimide comprises polyimide molecules of a structure represented by the chemical formula (2c):

wherein T, PI and Y are groups to be indicated next, respectively, that is,
   T represents a divalent aromatic group selected from the group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group;
   PI represents a polyimide backbone; and
   Y represents a trivalent aromatic group selected from the group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

(5) A crosslinkable-group-containing polyimide as described above under (3) or (4), wherein in the chemical formula (2b) or (2c), T is the following chemical formula (2d) :

(6) A crosslinkable-group-containing polyimide as described above under any one (3)-(5), wherein in the chemical formula (2a) or (2c), Y is the following chemical formula (2e) :

(7) A crosslinkable-group-containing polyimide as described above under any one of (1)-(6), wherein a backbone of the polyimide has recurring structural units represented by the chemical formula (1):

wherein Ar and R are groups to be described next, that is,
   Ar represents a divalent aromatic group selected from' the group consisting of:

   wherein J represents a divalent linking group selected from the group consisting of a carbonyl group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group, K represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group, p and q each independently stand, for 0 or 1, and a position of each bond, said position being unspecified, is a para-position or meta-position; and
   R represents a tetravalent aromatic group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group.

(8) A crosslinkable-group-containing polyimide as described above under claim 7, wherein 50 to 100 mole % of the recurring structural units represented by the chemical formula (1) are of a recurring unit structure represented by the chemical formula (1a):

wherein G is a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group.

(9) A crosslinkable-group-containing polyimide as described above, under (8), wherein in the chemical formula (1a), G is 4'-oxy-4-biphenoxy group.

(10) A crosslinkable-group-containing polyimide as de. scribed above under (8), wherein in the chemical formula (1a), G is a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group.

(11) A crosslinkable-group-containing polyimide as described above under (7), wherein 50 to 100 mole % of the recurring structural units represented by the chemical formula (1) are of a recurring unit structure represented by the chemical formula a (1b):

wherein X and R are groups to be indicated next, respectively, that is,
   X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group; and
   R represents a tetravalent linking group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulf one group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group, and a position of each bond, said position being unspecified, is a para-position or meta-position.

(12) A crosslinkable-group-containing polyimide as described above under (11), wherein in the chemical formula (1b),
   X is an oxygen atom;
   imido-bonded positions of two benzenes to which X is directly bonded are a m-position and a para-position, respectively; and
   R is a 3,'4',3',4'-substituted biphenyl.

(13) A crosslinkable-group-containing polyimide as described above under (7), wherein among the recurring structural units represented by the chemical formula (1), 50 to 100 mole % are of a recurring unit structure represented by the chemical formula (1c):

wherein X and R are groups to be indicated next, respectively, that is,
   X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group; and
   R represents a tetravalent linking group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group, and a position of each bond, said position being unspecified, is a para-position or meta-position.

(14) A crosslinkable-group-containing polyimide as described above under (13), wherein in the chemical formula (1c), X is an oxygen atom.

(15) A crosslinkable-group-containing polyimide as described above under (13), wherein in the chemical formula (1c),
   X is an oxygen atom;
   positions of a benzene ring, at which two Xs are directly bonded, respectively, are m-positions relative to each other;
   bonded positions of each of two benzenes to each of which X and an imido group are directly bonded are p-positions relative to each other; and
   R is a 3,4,3',4'-substituted biphenyl.

(16) A crosslinkable-group-containing polyimide as described above under (7), wherein among the recurring structural units represented by the chemical formula (1), 50 to 100 mole % are of a recurring unit structure represented by the chemical formula (1e):

wherein Q, Z and R are groups to be indicated next, respectively, that is,
   Q represents a divalent aromatic group selected from the group consisting of an ether group and an isopropylidene group;
   Z represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, and

   R represents a tetravalent aromatic group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group, and a position of each bond, said position being unspecified, is a para-position or meta-position.

(17) A crosslinkable-group-containing polyimide as described above under (16), wherein in the chemical formula (1e),
   Q is an oxygen atom; and
   Z is at least one divalent group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

(18) A crosslinkable-group-containing polyimide as described above under (16), wherein in the chemical formula (1e),

Q

is an oxygen atom;

Z

is a direct bond; and

R

is a 1,2,4,5-substituted benzene.

(19) A process for the production of a melt-moldable or formable, crosslinkable-group-containing polyimide, 1 to 80 mole % of molecule ends of the polyimide being crosslinkable-group-containing molecule ends represented by a chemical formula (2a) and 99 to 20 mole % of the molecule ends being crosslinkable-group-free molecule ends represented by a chemical formula (2b), which comprises end-blocking ends of polyimide backbones by using dicarboxylic acid anhydrides represented by the chemical formula (3a) and the chemical formula (3b):

wherein Y represents a trivalent aromatic group selected from the group consisting:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group;

wherein T represents a divalent aromatic group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group;

wherein Y represents a trivalent aromatic group selected from the group consisting:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group; and

wherein T represents a divalent aromatic group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

(20) A process as described above under (19), wherein the dicarboxylic acid anhydrides represented by the chemical formula (3a) and the chemical formula (3b) are used in amounts represented, on a molar ratio basis, by the numerical formula [1]:
   1/99 ≦ the dicarboxylic acid anhydride represented by the chemical formula (3a)/the dicarboxylic acid anhydride represented by the chemical formula (3b) ≦ 80/20 [1]

   Y represents a trivalent aromatic group selected from the group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

   T represents a divalent aromatic group selected from the group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

(21) A process as described above under (19) or (20), wherein in the chemical formula (3a) and/or the chemical formula (3b), T is the chemical formula (2a) and/or Y is the chemical formula (2e):

(22) A process as described above under any one of (19)-(21), wherein the polyimide backbones have been obtained by thermally and/or chemically imidating a polyamic acid obtained as a polyimide precursor by polymerizing a diamine component and a tetracarboxylic acid anhydride component.

(23) A process as described above under (22), wherein the diamine component is at least one diamine component selected from the group consisting of diamine components represented by the chemical formula (4):

        H₂N―Ar―NH₂     (4)

wherein Ar represents a divalent aromatic group selected from the group consisting of:

wherein J represents a divalent linking group selected from the group consisting of a carbonyl group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group, K represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group, p and q each independently stand for 0 or 1, and a position of each bond, said position being unspecified, is a para-position or meta-position;

(24) A process as described above under (23), wherein of the diamine component represented by the chemical formula (4), 50 to 100 mole % are represented by the chemical formula (4c):

wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group, and a position of each bond, said position being unspecified, is a para-position or meta-position.

(25) A process as described above under (24), wherein in the chemical formula (4c), X is an oxygen atom.

(26) A process as described above under (24), wherein in the chemical formula (4c);
   X is an oxygen;
   positions of a benzene ring, at which two Xs are directly bonded, respectively, are m-positions relative to each other; and
   bonded positions of each of two benzenes to each of which X and an amino group are directly bonded are p-positions relative to each other.

27. A process as described above under (24), wherein of the diamine component represented by the chemical formula (4), 50 to 100 mole % are represented by the chemical formula (4d) :

wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

(28) A process as described above under (27), wherein in the chemical formula (4d), X is a direct bond.

(29) A process as described above under (22), wherein the tetracarboxylic acid dihydride component is represented by the chemical formula (5):

wherein R represents a tetravalent linking group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group.

(30) A crosslinkable-group-containing polyimide as described above under any one of (1)-(18), there is a temperature T [°C] which simultaneously satisfy the following numerical formulas [2] and [3]:



where

MV5(T):

melt viscosity [Pa·sec] of the polyimide as measured under a desired constant shearing stress in a range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at a temperature T [°C] for 5 minutes; and

MV30(T):

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at the temperature T [°C] for 30 minutes.

(31) A crosslinkable-group-containing polyimide as described above under any one of (1)-(18), wherein there is a temperature T [°C] which simultaneously satisfy the following numerical formulas [2], [3] and [4]:





where

MV5(T):

melt viscosity [Pa·sec] of the polyimide as measured under a desired constant shearing stress in a range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at a temperature T [°C] for 5 minutes;

MV5(T+20) :

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at a temperature T+20 [°C] for 5 minutes;

MV30(T):

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at the temperature T [°C] for 30 minutes.

MV30 (T+20) :

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at a temperature T+20 [] for 30 minutes.

(32) A crosslinkable-group-containing polyimide as described above under any one of (1)-(18), which simultaneously satisfies the following numerical formulas [5] and [6]:



where

MV5(360):

melt viscosity [Pa·sec] of the polyimide as measured under a desired constant shearing stress in a range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at 360 [°C] for 5 minutes; and

MV30(360) :

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at 360 [°C] for 30 minutes.

(33) A crosslinkable-group-containing polyimide as described above under any one of (1)-(18), wherein a time t (min) which satisfies the numerical formula [7] lasts 10 minutes or longer:

where

G' (t) :

storage modulus of the polyimide as measured at 360°C and 1 Hz after an elapse of the time t (min) ; and

G" (t):

loss modulus of the polyimide as measured at 360°C and 1 Hz after an elapse of the time t (min).

(34) A crosslinked polyimide obtained by heat-treating a crosslinkable-group-containing polyimide as described above under any one of (1)-(18) and (30)-(33).

(35) A solution or suspension comprising a crosslinkable-group-containing polyimide as described above under any one of (1)-(18) and (30)-(33).

[0017] The polyimide according to the present invention is a crosslinkable-group-containing polyimide which contains crosslinking groups at 1 to 80 mole % of molecule ends thereof.

[Molecule ends]

[0018] The term "molecule ends" as used herein means molecule ends, which are not contained in recurring structural units of a polyimide molecule chain arid schematically correspond to "-End"s in the chemical formula (6a).

[0019] Where, as will be indicated by the chemical, formula (6b), two kinds of units A and B exist in a recurring structural unit and the number of units of one kind ("A" in this case) is greater by one than that of the unit(s) of the other kind, molecule ends schematically corresponds to "-End"s in the chemical formula (6b).

[0020] It is to be noted that the structural unit A or B is not supposed to be contained in the structure of each "-End".

[Crosslinkable groups]

[0021] The term "crosslinkable groups" means groups capable of forming a certain bond between molecule chains as a result of a reaction between crosslinkable groups or a crosslinkable group and a group on a polyimide backbone under specific crosslinking conditions. In the present invention, crosslinkable groups exist in molecule ends of polyimide chains.

[0022] No limitation is imposed on the crosslinking conditions, and a known crosslinking reaction such as heat-setting or photo-setting can be applied. From the standpoint of use, preferred are crosslinkable groups to which conditions not decomposing a polyimide backbone under crosslinking conditions are applicable.

[0023] If crosslinkable groups react with groups on a polyimide backbone, groups usable as the crosslinkable groups obviously differ depending on the polyimide backbone to be used.

[0024] As crosslinkable groups, those known to the public can be chosen and used as No limitation is imposed on the kind of crosslinkable groups, but representative examples can include ethynyl groups, benzocyclobuten-4'-yl groups, vinyl groups, allyl groups, cyano groups, isocyanate groups, nitrilo groups, amino groups, isopropenyl groups, vinylene groups, vinylidene groups, ethynylidene groups, and biphenylenyl groups.

[Molecule ends having preferred crosslinkable groups]

[0025] Molecule ends, each of which is usable in the present invention and has a crosslinkable group, are preferably those represented by the chemical formula (2a). The polyimide according to the present invention is characterized in that 1 to 80 mole % of the total number of end groups of the polymer chain are such crosslinkable-group-containing end groups and 99 to 20 mole % are crosslinkable-group-free end groups, preferably, those represented by the chemical formula (2b).

[0026] Specific examples of end structures represented by the chemical formula (2a) can include:

[0027] Incidentally, the crosslinkable-group-containing end groups are not limited to those exemplified above, but known crosslinkable-group-containing end groups can be used either singly or in combination as desired.

[0028] As the most preferred crosslinkable-group-containing end group, one of the chemical formula (2a) in which Y is the chemical formula (2e) is used. Specifically, it is:

[Crosslinkable-group-free molecule ends]

[0029] As the crosslinkable-group-containing polyimide according to the present invention is characterized in that it has crosslinkable groups at 1 to 80 mole % of its molecule ends, 99 to 20 mole % of its molecule ends are crosslinkable-group-free molecule ends. The term "crosslinkable-group-free molecule ends" ineans molecule end groups which cannot form any bond between molecule chains because no reaction takes place between the molecule ends themselves or the molecule ends and groups on polyimide backbones under any conditions during a molding or forming step, a post treatment step or the like.

[Crosslinkable-group-containing molecule ends which may function as crosslinkable-group-free molecule ends]

[0030] As the term "crosslinkable-group-free molecule ends" as used herein means molecule end groups incapable of crosslinking under any conditions during a molding or forming step, a post treatment step or the like as described above, a structure which becomes a crosslinkable group under certain conditions can function as a crosslinkable-group-free group when employed under conditions milder than the first-mentioned conditions.

[Preferred crosslinkable-group-free molecule ends]

[0031] As crosslinkable-group-free molecule ends, those of known structures can be used either singly or in combination, and no limitation is imposed. Nonetheless, use of those represented by the chemical formula (2) is preferred. Most preferably, those of the chemical formula (2) in which T represents the chemical formula (2d) are used. Specifically, it is:

[Molar ratio of crosslinkable-group-containing molecule ends to crosslinkable-group-free molecule ends]

[0032] The present invention relates to the crosslinkable-group-containing polyimide characterized in that it contains crosslinkable groups at 1 to 80 mole % of its molecule ends. It is therefore essential that the molar ratio of crosslinkable-group-containing molecule ends to crosslinkable-group-free molecule ends falls within the following range:

where

[E'1]:

the molar quantity of the crosslinkable-group-containing molecule ends; and

[E'2] :

the molar quantity of the crosslinkable-f-group-free molecule ends.

[0033] If the value of [E'1]/[E'2] falls short of this range and is smaller than 1/99, no sufficient crosslinking density can be achieved, leading to insufficient improvements in chemical resistance, heat resistance and mechanical properties. If the value of [E'1]/[E'2] is greater than 80/20, on the other hand, a sufficient crosslinking density is available, but upon melt molding or forming, a substantial viscosity increase takes place so that the melt molding or forming becomes infeasible.

[0034] The range of the [E'1]/[E'2] value has to be chosen appropriately depending on molding or forming conditions. In general, however, the preferred range is:

and the more preferred range is:

[0035] The still more preferred range varies depending on the molding or forming process. For example, in a batchwise molding or forming process, such as compression molding, that involves residence, in a molten state, the still more preferred range is:

and the most preferred range is:

[0036] For example, in a molding or forming process, such as injection molding or extrusion, that involves residence in a molten state and requires a continuous operation, the preferred range is:

and the most preferred range is:

[0037] For example, in a molding or forming process that does not involve much residence in a molten state, the preferred range is:

and the most preferred range is:

[Structure of the crosslinkable-group-containing polyimide]

[0038] To form the backbone structure of the crosslinkable-group-containing polyimide according to the present invention, known polyimides are used singly, as a blend of a desired ratio, or as a copolymer of a desired ratio.

[Structure of preferred crosslinkable-group-containing polyimide - (1)]

[0039] Although no limitation is imposed on the backbone structure of the crosslinkable-group-containing polyimide. according to the present invention, preferred is a crosslinkable-group-containing polyimide characterized in that the backbone structure, which makes up the crosslinkable-group-containing polyimide, is substantially provided with thermoplasticity.

[What does "substantially provided with thermoplasticity" mean?]

[0040] The expression "a backbone structure is substantially provided with thermoplasticity" as used herein means that plasticity is shown as a characteristic property of the backbone structure, specifically that a polyimide, which has been obtained by polymerizing a polyimide of the backbone structure under diamine-excess conditions and then blocking molecular chains of the polyimide at ends thereof with phthalic anhydride in a stoichiometric or greater amount, shows thermoplasticity.

[Structure of preferred crosslinkable-group-containing polyimide - (2)]

[0041] Preferably, the polyimide is a crosslinkable-group-containing polyimide which permits melt molding or forming.

[Melt molding or forming]

[0042] The term "melt molding or forming" as used herein means. a molding or forming process of the polyimide, in at least one step of which the resin is caused to flow in a molten state. The molten state of the polyimide can be achieved only at a temperature higher than its crystal melting temperature or glass transition temperature. To allow a resin to flow, the resin is required to have an adequate melt viscosity which varies depending on shearing stress which in turn differs depending on the molding or forming process. Incidentally, the temperature, shearing stress and melt viscosity differ depending on the molding or forming process.

[0043] Illustrative of the molding or forming process are extrusion, injection molding, compression molding, blow molding, vacuum forming, rotational molding, reaction injection molding, laminated molding, and casting.

[Variations in melt viscosity]

[0044] To continuously perform processing under steady state, variations in melt viscosity are required to be small. The term "variations in melt viscosity" means variations in viscosity when a resin is held at a processing temperature under processing shearing stress.

[Melt viscosity]

[0045] From the foregoing, the polyimide according to the present invention is a crosslinkable-group-containing polyimide which, although no limitation is imposed on its viscosity, preferably satisfies the following numerical formulas [2] and [3] simultaneously:



where

MV5(T) :

melt viscosity [Pa·sec] of the polyimide as measured under a desired constant shearing stress in a range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at a temperature T [°C] for 5 minutes, and

MV30 (T):

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at the temperature T [°C] for 30 minutes;

   more preferably, satisfies the following numerical formulas [2], [3] and [4] simultaneously:





where

MV5 (T):

melt viscosity [Pa·sec] of the polyimide as measured under a desired constant shearing stress in a range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at a temperature T [°C] for 5 minutes,

MV5 (T+20) :

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at a temperature T+20 [°C] for 5 minutes,

MV30(T):

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at the temperature T [°C] for 30 minutes, and

MV30 (T+20)

: melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at a temperature T+20 [°C] for 30 minutes; and

   most preferably, satisfies the following numerical formulas [2], [3] and [4b] simultaneously:





where

MV5(T) :

melt viscosity [Pa·sec] of the polyimide as measured under' a desired constant shearing stress in a range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at a temperature T [°C] for 5 minutes,

MV5 (T+20) :

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at a temperature T+20 [°C] for 5 minutes,

MV30(T):

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at the temperature T [°C] for 30 minutes, and

MV30(T+20)

: melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at a temperature T+20 [°C] for 30 minutes.

[0046] When as crosslinkable-group-containing end groups, those of the structure represented by the chemical formula (2) are used, inclusion of 360°C within a range of the temperature T [°C] which satisfies the above numerical formulas [2], [3], [4] and [4b] is preferred from the additional consideration of the fact that the crosslinking temperature condition for the crosslinkable groups is about 360°C or higher.

[0047] In other words, the polyimide according to the present invention is a crosslinkable-group-containing polyimide which preferably satisfies the following numerical formulas [5] and [6] simultaneously:



where

MV5(360):

melt viscosity [Pa·sec] of the polyimide as measured under a desired constant shearing stress in a range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at 360 [°C] for 5 minutes, and

MV30(360):

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at 360 [°C] for 30 minutes;

   more preferably, satisfies the following numerical formulas [5], [6] and [8] simultaneously:





where

MV5(360):

melt viscosity [Pa·sec] of the polyimide as measured under a desired constant shearing stress in a range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at 360 [°C] for 5 minutes,

MV5(380):

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at 380 [°C] for 5 minutes,

MV30(360) :

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at 360 [°C] for 30 minutes,

MV30 (380) :

: melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at 380 [°C] for 30 minutes; and

   most preferably, satisfies the following numerical formulas [5], [6] and [8b] simultaneously:





where

MV5(360):

melt viscosity [Pa·sec] of the polyimide as measured under a desired constant shearing stress in a range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at 360 [°C] for 5 minutes,

MV5 (380) :

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at 380 [°C] for 5 minutes,

MV30 (360) :

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at 360 [°C] for 30 minutes,

MV30(380):

melt viscosity [Pa·sec] of the polyimide as measured under the desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing the polyimide to melt by holding the polyimide at 380 [°C] for 30 minutes.

[Measuring method of melt viscosity]

[0048] Although no particular limitation is imposed on the measuring method of a melt viscosity, the melt viscosity can be measured, for example, by a Koka-type flow tester (e.g., "CFT500A" manufactured by Shimadzu Corporation) under conditions of an orifice of 1.0 mm (diameter) x 10 mm (length) and a load of 100 kgf.

[0049] It is known (from "Rheology Measuring Methods" compiled by the Rheology Committee of the Society of Polymer Science, Japanese) that this case, shearing stress (Tw) [Pa] is determined by calculating apparent shear stress against a nozzle wall and the value so calculated is expressed by:

where

P: extrusion pressure [Pa];

R: nozzle diameter/2 [cm]; and

Lc: nozzle length [cm].

The shear stress measured by this measuring method is, therefore, 0.245 [MPa]

[Gel time]

[0050] As another parameter which also indicates whether or not a melt flow is feasible, gel time can be mentioned. The gel time of a resin at a given temperature is represented by t which satisfies the following numerical formula [7]:

where

G' (t) :

storage modulus of the resin as measured at the given temperature and a constant frequency after an elapse of the time t [min] ; and

G" (t):

loss modulus of the resin as measured at the given temperature and the constant frequency after an elapse of the time t (min).

[0051] No limitation is imposed on the gel time, because upon measuring the gel time, the sample temperature and the measuring frequency must be changed depending on the processing method and the properties of the resin. In the case of each polyimide in this application, however, the gel time measured at a constant sample temperature of 360°C and 1Hz may preferably be 10 [min] or longer;, with 20 [min] or longer being more preferred.

[0052] No particular limitation is imposed on the measuring methods of the storage modulus and loss modulus. As an example, however, they can be measured by a melt viscoelasticity meter (e.g., "RDS-II" manufactured by Rheometrix Scientific F.E.) equipped with parallel plates (e.g., 25 mm disposable).

[Preferred structure of crosslinkable-group-containing polyimide - (3)]

[0053] More preferably, the crosslinkable-group-containing polyimide according to the present invention is a crosslinkable-group-containing polyimide containing molecule chains each of which has a crosslinkable-group-containing end at an end thereof and a crosslinkable-group-free end at an opposite end thereof. Although no limitation is imposed on the content.of the molecule chains; their content may be preferably 0.2 mole % or higher, more preferably 1 mole % or higher, most preferably 5 mole % or higher.

[0054] The crosslinkable-group-containing polyimide - which is characterized in that it contains molecule chains, each of which has a crosslinkable-group-containing end at an end thereof and a crosslinkable-group-free end at an opposite end thereof may more preferably be a crosslinkable-group-containing polyimide having the structure represented by the chemical formula (2c). Although no limitation is imposed on the content of the molecule chains in the polyimide either, their content may be preferably 0.2 mole % or higher, more preferably 1 mole % or higher, most preferably 5 mole % or higher.

[Preferred structure of crosslinkable-group-containing polyimide -(4)]

[0055] The crosslinkable-group-containing polyimide according to the present invention may preferably contain recurring structural units represented by the chemical formula (1) in the polyimide backbone.

[More preferred structure of crosslinkable-group-containing polyimide - (1)]

[0056] One of more preferred examples of the crosslinkable-group-containing polyimide according to the present invention which has recurring structural units represented by the chemical formula (1) is characterized in that 50 to 100 mole % of the recurring structural units are recurring structural units represented by the chemical formula (1a).

[0057] Among these, most preferred are crosslinkable-group-containing polyimides 50 to 100 mole % of the recurring structural units of each of which have one of the following structures:

[More preferred structure of crosslinkable-group-containing polyimide -(2)]

[0058] Another one of the more preferred examples of the crosslinkable-group-containing polyimide according to the present invention which has recurring structural units represented by the chemical formula. (1) is characterized in that 50 to 100 mole % of the recurring structural units are recurring structural units represented by the chemical formula (1b).

[0059] Among these, most preferred are crosslinkable-group-containing polyimides 50 to 100 mole % of the recurring structural units of each of which have the following structure:

[More preferred structure of crosslinkable-group-containing polyimide - (3)]

[0060] A further one of the more preferred examples of the crosslinkable-group-containing polyimide according to the present invention which has recurring structural units represented by the chemical formula (1) is characterized in that 50 to 100 mole % of the recurring structural units are recurring structural units represented by the chemical formula (1c).

[0061] Among these, preferred are crosslinkable-group-containing polyimides 50 to 100 mole % of the recurring structural units of each of which has the chemical formula (1c) in which X is an oxygen atom, and most preferred are crosslinkable-group-containing polyimides 50 to 100 mole % of the recurring structural units of each of which has a structure represented by:

[More preferred structure of crosslinkable-group-containing polyimide - (4)]

[0062] A still further one of the more preferred examples of the crosslinkable-group-containing polyimide according to the present invention which has recurring structural units represented by the chemical formula (1) is characterized in that 50 to 100 mole % of the recurring structural units are recurring structural units represented by the chemical formula (1e).

[0063] Among these, preferred are crosslinkable-group-containing polyimides 50'to 100 mole % of the recurring structural units of each of which are recurring structural units represented by the following formula (1d) :

wherein X and R are groups to be indicated next, respectively, that is,
   X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group; and
   R represents a tetravalent aromatic group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group, and a position of each bond, said position being unspecified, is a para-position or meta-position.

[0064] Among these, preferred are crosslinkable-group-containing polyimides 50 to 100 mole % of the recurring structural units of each of which has the chemical formula (1d) in which Z2 is an oxygen atom, and most preferred are crosslinkable-group-containing polyimides 50 to 100 mole % of the recurring structural units of each of which has a recurring unit structure represented by:

[Molecular weight of crosslinkable-group-containing polyimide]

[0065] As a measure of the molecular weight of a crosslinkable-group-containing polyimide, a logarithmic viscosity number is used.

[Logarismic viscosity number of crosslinkable-groupcontaining polyimide]

[0066] The logarithmic viscosity number of a crosslinkable-group-containing polyimide is in a range of from 0.1 to 1.5 dL/g. A logarithmic viscosity number smaller than 0.1 leads to a decrease in the molecular weight between crosslinking points and hence to substantial reductions in mechanical properties, while a logarithmic viscosity number higher than 1.5 leads to an increase in melt viscosity and thus to a considerable reduction, in melt moldability or formability. The preferred logarithmic viscosity number is in a range of from 0.2 to 1.2, with a range of from 0.3 to 0.8 being more preferred, and a range of from 0.4 to 0.6 being most preferred.

[Measuring method of logarithmic viscosity number]

[0067] The above-described logarithmic viscosity number can be measuring in a 9:1 by weight mixed solvent of p-chlorophenol and phenol, at a solution viscosity of 0.5 g/100 mL and 35°C, by using, for example, a Ubbellohde viscometer.

[Regularity when the crosslinkable-group-containing polyimide is a copolymer]

[0068] When the crosslinkable-group-containing polyimide according to the present invention is a copolymer, a limitation may be imposed or may not be imposed on the specific order or regularity of recurring units of two or more kinds which make up the copolymer. Concerning the kind of the copolymer, the copolymer can be of any one of random, alternating and block structures.

[Production process of crosslinkable-group-containing polyimide]

[0069] A detailed description will hereinafter be made of the process for the production of the crosslinkable-group-containing polyimide according to the present invention. However, it should be borne in mind that no limitation is imposed on the production process in the present invention.

[Raw materials to be used]

[0070] The crosslinkable-group-containing polyimide according to the present invention is generally obtained from the following raw materials:

(A) a diamine component;

(B) a tetracarboxylic acid dianhydride component;

(C) an end blocking agent having a crosslinkable group; and

(D) an end blocking agent having no crosslinkable group.

[Diamine component]

[0071] The diamine component usable to obtain the crosslinkable-group-containing polyimide according to the present invention can preferably be, but is not limited to, an aromatic diamine.

[0072] Examples of the diamine component can include:

a) Diamines containing one benzene ring:

p-phenylenediamine, and

m-phenylenediamine;

b) Diamines containing two benzene rings:

3,3'-diaminodiphenyl ether,

3,4'-diaminodiphenyl ether,

4,4'-diaminodiphenyl ether,

3,3'-diaminodiphenyl sulfide,

3,4'-diaminodiphenyl sulfide,

4,4'-diaminodiphenyl sulfide,

3,3'-diaminodiphenyl sulfone,

3,4'-diaminodiphenyl sulfone,

4,4'-diaminodiphenyl sulfone,

3,3'-diaminobenzophenone

4,4'-diaminobenzophenone,

3,4'-diaminobenzophenone,

3,3'-diaminodiphenylmethane,

4,4'-diaminodiphenylmethane,

3,4'-diaminodiphenylmethane,

2,2-di(3-aminophenyl)propane,

2,2-di(4-aminophenyl)propane,

2-(3-aminophenyl)-2-(4-aminophenyl)propane,

2,2-di(3-aminophenyl)-1,1,1,3,3,3,-hexafluoropropane,

2,2-di(4-aminophenyl)-1,1,1,3,3,3,-hexafluoropropane,

2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3,-hexafluoropropane,

1,1-di(3-aminophenyl)-1-phenylethane,

1,1-di(4-aminophenyl)-1-phenylethane, and

1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane;

c) Diamines containing three benzene rings:

1,3-bis(3-aminophenoxy)benzene,

1,3-bis(4-aminophenoxy)benzene,

1,4-bis(3-aminophenoxy)benzene

1,4-bis(4-aminophenoxy)benzene,

1,3-bis(3-aminobenzoyl)benzene,

1,3-bis(4-aminobenzoyl)benzene,

1,4-bis(3-aminobenzoyl)benzene,

1,4-bis(4-aminobenzoyl)benzene,

1,3-bis(3-amino-α,α-dimethylbenzyl)benzene,

1,3-bis(4-amino-α,α-dimethylbenzyl)benzene,

1,4-bis(3-amino-α,α-dimethylbenzyl)benzene,

1,4-bis(4-amino-α,α-dimethylbenzyl)benzene,

1,3-bis(3-amino-α,α-ditrifluoromethylbenzyl)-benzene,

1,3-bis(4-amino-α,α-ditrifluoromethylbenzyl)-benzene,

1,4-bis(3-amino-α,α-ditrifluoromethylbenzyl)-benzene,

1,4-bis(4-amino-α,α-ditrifluoromethylbenzyl)-benzene,

2,6-bis(3-aminophenoxy)benzonitrile, and

2,6-bis(3-aminophenoxy)pyridine;

d) Diamines containing four benzene rings:

4,4'-bis(3-aminophenoxy)biphenyl,

4, 4'-bis (4-aminophenoxy)biphenyl,

bis[4-(3-aminophenoxy)phenyl ketone,

bis[4-(4-aminophenoxy)phenyl] ketone,

bis[4-(3-aminophenoxy)phenyl]sulfide,

bis[4-(4-aminophenoxy)phenyl] sulfide,

bis[4-(3-aminophenoxy)phenyl] sulfone,

bis[4-(4-aminophenoxy)phenyl] sulfone,

bis [4-(3-aminophenoxy)phenyl] ether,

bis [4-(4-aminophendxy)phenyl] ether,

2,2-bis[4-(3-aminophenoxy)phenyl]propane,

2,2-bis[4-(4-aminophenoxy)phenyl]propane,

2,2-bis [3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and

2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane;

e) Diamines containing five benzene rings:

1, 3-bis [4-(3-aminophenoxy)benzoyl]benzene,

1,3-bis[4-(4-aminophenoxy)benzoyl]-benzene,

1,4-bis[4-(3-aminophenoxy)benzoyl]benzene,

1,4-bis[4-(4-aminophenoxy)benzoyl]benzene,

1,3-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]-benzene,

1,3-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]-benzene,

1,4-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]-benzene, and

1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]-benzene;

f) Diamines containing six benzene rings:

4,4'-bis[4-(4-aminophenoxy)benzoyl]diphenyl ether,

4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]-benzophenone,

4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]-diphenyl sulfone, and

4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenyl sulfone;

g) Diamines containing aromatic substituent group(s):

3,3'-diamino-4,4'-diphenoxybenzophenone,

3,3'-diamino-4,4'-dibiphenoxybenzophenone,

3,3'-diamino-4-phenoxybenzophenone, and

3,3'-diamino-4-biphenoxybenzophenone; and

h) Diamines, containing a spirobiindane ring:

6,6'-bis(3-aminophenoxy)3,3,3',3'-tetramethyl-1,1'-spirobiindane, and:

6,6'-bis(4-aminophenoxy)3,3,3',3'-tetramethyl-1,1'-spirobiindane.

[0073] Also usable are diamines each of which is obtained by substituting some or all of the hydrogen atoms on one or more of the aromatic ring(s) of the corresponding one of the above-described diamines by a like number of substituent group(s) selected from fluoro, methyl, methoxy, trifluoromethyl or trifluoromethoxy groups.

[0074] Further, these diamines are also usable after in place of some or all of the hydrogen atoms on one or more of the aromatic ring(s) of each of the diamines, a like number of ethynyl group(s), benzocyclobuten-4'-yl group(s), vinyl group(s), allyl group(s), cyano group(s), isocyanate group(s), nitrilo group(s) and/or isopropenyl group(s), which can act as crosslinking points, are introduced as substituent group(s), preferably to an extent not impairing the moldability or formability. Moreover, one or more of vinylene groups, vinylidene groups and ethynylidene groups, which can act as crosslinking points, can be incorporated into each backbone skeleton, rather than as substituent group (s), preferably to an extent not impairing the moldability or formability.

[0075] In addition, for the purpose of achieving improvements in or modifications to performance, copolymerization can be conducted using one or more aliphatic diamines, to an extent not impairing various good physical properties, together with the above-described diamine. Examples of such aliphatic diamines can include:

i) Siloxanediamines:

1,3-bis(3-aminopropyl)tetramethyldisiloxane,

1,3-bis(4-aminobutyl)tetramethyldisiloxane,

α,ω-bis(3-aminopropyl)polydimethylsiloxane, and

α,ω-bis(3-aminobutyl)polydimethylsiloxane;

j) Ethyleneglycoldiamines:

bis(aminomethyl) ether;

bis(2-aminoethyl) ether,

bis(3-aminopropyl) ether,

bis(2-aminomethoxy)ethyl] ether,

bis[2-(2-aminoethoxy)ethyl] ether,

bis[2-(3-aminoprotoxy)ethyl] ether,

1,2-bis(aminomethoxy)ethane,

1,2-bis(aminoethoxy)ethane,

1,2-bis[2-(aminomethoxy)ethoxy]ethane,

1,2-bis[2-(2-aminomethoxy)ethoxy]ethane,

ethylene glycol bis(3-aminopropyl) ether,

diethylene glycol bis(3-aminopropyl) ether, and

triethylene glycol bis(3-aminopropyl) ether;

k) Methylenediamines:

1,3-diaminopropane,

1,4-diaminobutane,

1,5-diaminopentane,

1,6-diaminohexane,

1,7-diaminoheptane,

1,8-diaminooctane,

1,9-diaminononane,

1,10-diaminodecane,

1,11-diaminoundecane, and

1,12-diaminododecane; and

l) Alicyclic diamines:

1,2-diaminocyclohexane,

1,3-diaminocyclohexane,

1,4-diaminocyclohexane,

1, 2-di(2-aminoethyl)cyclohexane,

1,3--di(2-aminoethyl)cyclohexane,

1,4-di(2-aminoethyl)cyclohexane,

bis(4-aminocyclohexyl)methane,

2,6-bis(aminomethyl)bicyclo[2.2.1]heptane, and

2,5-bis(aminomethyl)bicyclo[2.2.1]heptane.

[0076] These diamines can be used either singly or in combination as needed.

[Preferred diamine components]

[0077] Among the above-exemplified diamine components, preferred diamines are those represented by the chemical formula (4).

[More preferred diamine components (1)]

[0078] Among the diamines represented by the chemical formula (4), diamines of a more preferred type are those represented by the chemical formula (4c). When these more preferred diamine compohents are used, it is particularly preferred to use them in a proportion of 50 to 100 mole %.

[0079] Usable examples of the diamines represented by the chemical formula (4c) can include:

1,3-bis (3-aminophenoxy)benzene,

1,3-bis(4-aminophenoxy)benzene,

1,4-bis(3-aminophenoxy)benzene,

1,4-bis(4-aminophenoxy)benzene,

1,3-bis(3-aminobenzoyl)benzene,

1,3-bis(4-aminobenzoyl)benzene,

1,4-bis(3-aminobenzoyl)benzene,

1,4-bis(4-aminobenzoyl)benzene,

1,3-bis(3-amino-α,α-dimethylbenzyl)benzene,

1,3-bis(4-amino-α,α-dimethylbenzyl)benzene,

1,4-bis(3-amind-α,α-dimethylbenzyl)benzene,

1,4-bis(4-amino-α,α-dimethylbenzyl)benzene,

1,3-bis(3-amino-α,α-ditrifluoromethylbenzyl)-benzene,

1,3-bis(4-amino-α,α-ditrifluoromethylbenzyl)-benzene,

1,4-bis(3-amino-α,α-ditrifluoromethylbenzyl)-benzene,

1, 4-bis(4-amino-α,α-ditrifluoromethylbenzyl)-benzene,

2,6-bis(3-aminophenoxy)benzonitrile, and

2,6-bis(3-aminophenoxy)pyridine.

[0080] Among these, particularly preferred diamines are:

1,3-bis(3-aminophenoxy)benzene,

1,3-bis(4-aminophenoxy)benzene,

1,4-bis(3-aminophenoxy)benzene,

1,4-bis(4-aminophenoxy)benzene,

1,3-bis(3-aminobenzoyl)benzene,

1,3-bis(4-aminobenzoyl)benzene,

1,4-bis(3-aminobenzoyl)benzene, and

1,4-bis(4-aminobenzoyl)benzene; and

   the most preferred diamine is:
   1,3-bis(4-aminophenoxy)bezene.

[More preferred diamine components (2)]

[0081] Among the diamines represented by the chemical formula (4), diamines of another more preferred type are those represented by the chemical formula (4d). When these more preferred diamine components are used, it is particularly preferred to use them in a proportion of 50 to 100 mole %.

[0082] Examples of the diamines represented by the chemical formula (4d) can include:

4,4'-bis(3-aminophenoxy)biphenyl,

bis[4-(3-aminophenoxy)phenyl] ketone,

bis[4-(3-aminophenoxy)phenyl] sulfide,

bis[4-(3-aminophenoxy)phenyl] sulfone,

bis[4-(3-aminophenoxy)phenyl] ether,

2,2-bis[4-(3-aminophenoxy)phenyl]propane, and

2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane.

[0083] Among these, the particularly preferred diamine component is:
   4,4'-bis(3-aminophenoxy)biphenyl.

[Tetracarboxylic acid dianhydride component]

[0084] No limitation is imposed on the tetracarboxylic acid dianhydride component employed to obtain the polyimide according to the present invention, and the following illustrative tetracarboxylic, acid dianhydrides can be used either singly or in combination as desired:

pyromellitic dianhydride,

3,3'4,4'-biphenyltetracarboxylic acid dianhydride,

3,3'4,4'-benzophenonetetracarboxylic acid dianhydride,

bis(3,4-dicarboxyphenyl) ether dianhydride,

bis(3,4-dicarboxyphenyl) sulfide dianhydride,

bis(3,4-dicarboxyphenyl) sulfone dianhydride,

2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,

2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride,

1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride,

1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride,

4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride,

2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride,

2,3,6,7-naphthalenetetracarboxylic acid dianhydride,

1,4,5,8-naphthalenetetracarboxylic acid dianhydride,

ethylenetetracarboxylic acid dianhydride,

butanetetracarboxylic acid dianhydride,

cyclopentanecarboxylic acid dianhydride,

2,2',3,3'-bezophenonetetracarboxylic acid dianhydride,

2,2',3,3'-biphenyltetracarboxylic acid dianhydride,

2,2-bis(2,3-dicarboxyphenyl)propane dianhydride,

2,2-bis (2, 3-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride,

bis(2,3-dicarboxyphenyl) ether dianhydride,

bis(2,3-dicarboxyphenyl) sulfide dianhydride,

bis(2,3-dicarboxyphenyl) sulfone dianhydride,

1,3-bis(2,3-dicarboxyphenoxy)benzene dianhydride,

1,4-bis(2,3-dicarboxyphenoxy)benzene dianhydride, and

1,2,5,6-naphthalenetetracarboxylic acid dianhydride.

[0085] In combination with all the kinds of the above-described tetracarboxylic acid dianhydride components, diamines in each of which some or all of the hydrogen atoms on one or more of the aromatic ring (s) have been replaced by a like number of substituent groups selected from fluoro groups, methyl groups, methoxy groups, trifluoromethyl groups and/or trifluoromethoxy groups can be used.

[0086] Further, the above-described diamines are also usable after in place of some or all of the hydrogen atoms on one or more of the aromatic ring(s) of each of the diamines, a like number of ethynyl group(s), benzocyclobuten-4,'-yl group(s), vinyl group(s), allyl group(s), cyano group(s), isocyanate group(s), nitrilo group(s) and/or isopropenyl group(s), which can act as crosslinking points, are introduced as substituent group (s), preferably to an extent not impairing the moldability or formability. Moreover, one or more of vinylene groups, vinylidene groups and ethynylidene groups, which can act as crosslinking points, can be incorporated into each backbone skeleton, rather than as substituent group(s), preferably to an extent not impairing the moldability or formability.

[0087] These tetracarboxylic acid dianhydride components can be used either singly or in combination as needed.

[0088] Depending on the production process, tetracarboxylic acid monoanhydrides, tetracarboxylic compounds other than anhydrides, or their derivatives such as salts can also be used as desired instead of such dianhydrides.

[Preferred tetracarboxylic acid dianhydride components]

[0089] Among the above-exemplified tetracarboxylic acid dianhydride components, preferred tetracarboxylic acid dianhydrides are tetracarboxylic acid dianhydrides represented by the chemical formula (5). Specific examples can include:

pyromellitic dianhydride,

3,3'4,4'-biphenyltetracarboxylic acid dianhydride,

3,3'4,4'-benzophenonetetracarboxylic acid dianhydride,

bis(3,4-dicarboxyphenyl) ether dianhydride,

bis(3,4-dicarboxyphenyl) sulfide dianhydride,

bis (3, 4-dicarboxyphenyl) sulfone dianhydride,

2,2-bis(3,4-dicarboxyphenyl)propane dianhydride,

2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride,

1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride,

1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride,

4,4'-bis(3,4-dicarboxyphenoxy)biphenyl dianhydride,

2,2-bis[(3,4-dicarboxyphenoxy)phenyl]propane dianhydride,

2,3,6,7-naphthalenetetracarboxylic acid dianhydride, and

1,4,5,8-naphthalenetetracarboxylic acid dianhydride,

[0090] [More preferred tetracarboxylic acid dianhydride components]

[0091] Among the diamines represented by the chemical formula (5), more preferred tetracarboxylic acid dianhydrides can be :

pyromellitic dianhydride,

3,3'4,4'-biphenyltetracarboxylic acid dianhydride,

3,3'4,4'-benzophenonetetracarboxylic acid dianhydride,

bis(3,4-dicarboxyphenyl) ether dianhydride,

bis(3,4-dicarboxyphenyl)sulfide dianhydride,

bis(3,4-dicarboxyphenyl) sulfone dianhydride,

2,2-bis(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropane dianhydride, and

1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride.

One or more tetracarboxylic acid dianhydride components selected from the group consisting of these more preferred tetracarboxylic acid dianhydrides can be used.

[Amount of the tetracarboxylic acid dianhydride component to be used]

[0092] The total amount of the tetracarboxylic acid dianhydride is from 0.8 to 1.25 moles per mole of the total amount of the diamine component to be used. By changing this molar ratio, the molecular weight of the resulting crosslinkable-group-containing polyimide can be controlled. A molar ratio lower than 0.8 cannot provide a molecular weight high enough to bring about sufficient properties, while a molar ratio higher than 1.25 leads to a reduction in the molecular weight.

[0093] When a dicarboxylic acid or its anhydride or derivative is used as an end blocking agent, the total amount of the tetracarboxylic acid dianhydride component may be preferably from 0.8 to 0.99, more preferably from 0.85 to 0.97 per mole of the total amount of the diamine component to be used, with a range of from 0.90 to 0.95 being most preferred.

[0094] In this case, use of a tetracarboxylic acid dianhydride component beyond the above range results in insufficient end blocking, thereby causing adverse effects on the thermal stability and moldability or formability.

[0095] When a monoamine is used as an end blocking agent, the total amount of the tetracarboxylic acid dianhydride component to be used may be preferably from 1.01 to 1.25 moles, more preferably from 1.05 to 1.20 moles per mole of the total amount of the diamine component to be used, with a range of from 1.07 to 1.15 being most preferred.

[0096] In this case, use of a tetracarboxylic acid dianhydride component below the above range results in insufficient end blocking, thereby causing adverse effects on the thermal stability and moldability or formability.

[0097] The control of the molecular weight of the crosslinkable-group-containing polyimide can be achieved by adjusting the molar ratio of the total amount of the tetracarboxylic acid dianhydride component to the total amount of the diamine component to be used. Depending on the polymerization process, the kind of the solvent, the polymerization time, the polymerization time and the like, however, their optimum charging ratio may differ in some instances.

[Crosslinkable-group-containing end blocking agent]

[0098] No limitation is imposed on the crosslinkable-group-containing end blocking agent to be used in the present invention. Crosslinkable-group-containing end blocking agents of various kinds are usable depending on the synthesis process of the polyimide, including monoamines and dicarboxylic acid anhydrides as representative examples. As crosslinkable group(s) to be introduced, a variety of known crosslinkable groups can be selected in accordance with molding or forming conditions.

[0099] Although no limitation is imposed on the kind of the crosslinkable group(s), representative examples can include ethynyl group, benzocyclobuten-4'-yl group, vinyl group, allyl group, cyano group, isocyanate group, nitrilo group, amino group, isopropenyl group, vinylene group, vinylidene group, and ethynylidene group.

[Preferred crosslinkable-group-containing end blocking agents]

[0100] The crosslinkable-group-containing end blocking agent usable in the present invention may preferably be a crosslinkable-group-containing dicarboxylic acid anhydride. Depending on the synthesis process, its ring-opened product or its derivative such as its salt can be used.

[0101] Examples can include:

• unsaturated aliphatic dicarboxylic acid anhydrides represented by maleic anhydride and nadic anhydride,
• ethynyl-containing dicarboxylic acid anhydrides, represented by 1-phenyl-2-(3,4-dicarboxyphenyl)-acetylene anhydride, ethynylphthalic anhydride and 6-ethynyl-2,3-dicarboxynaphthalene anhydride, and
• phthalic acid anhydrides or 2,3-dicarboxynaphthalene anhydride derivatives containing a benzocyclobuten-4'-yl group, vinyl group, allyl group or isopropenyl group.

[End blocking agents containing more preferred crosslinking group]

[0102] The crosslinkable group contained in the structure may preferably be an ethynyl group, with one containing a phenylethynylbenzene structure being more preferred. [End blocking agents containing still more preferred crosslinking group]

[0103] The crosslinkable-group-containing end blocking agent usable in the present invention may more preferably be a dicarboxylic acid anhydride represented by the chemical formula (3a)

[0104] Specific examples are:

1-phenyl-2- (3, 4-dicarboxyphenyl)acetylene anhydride,

1-phenyl-2-(3-(3,4-dicarboxyphenoxy)phenyl)acetylene anhydride,

1-phenyl-2-(3-(3,4-dicarboxyphenylcarbonyl)phenyl)acetylene anhydride,

1-phenyl-2-(3-(3,4-dicarboxyphenylsulfonyl)phenyl)acetylene anhydride,

1-phenyl-2-(3-(3,4-dicarboxyphenylsulfinyl)phenyl)acetylene anhydride,

1-phenyl-2-(3-(2-(3,4-dicarboxyphenyl)isopropanyl)phenyl)-acetylene anhydride,

1-phenyl-2-(3-(1,1,1,3,3,3-hexafluoro-2-(3,4-dicarboxyphenyl)isopropanyl)phenyl)acetylene anhydride,

1-phenyl-2-(3-(3,4-dicarboxyphenyl)phenyl)acetylene anhydride,

1-phenyl-2-(4-(3,4-dicarboxyphenyl)phenyl)acetylene anhydride,

1-phenyl-2-(4-(3,4-dicarboxyphenylcarbonyl)phenyl)acetylene anhydride,

1-phenyl-2-(4-(3,4-dicarboxyphenylsulfonyl)phenyl)acetylene anhydride,

1-phenyl-2-(4-(3,4-dicarboxyphenylsulfinyl)phenyl)acetylene anhydride,

1-phenyl-2-(4-(2-(3,4-dicarboxyphenyl)isopropanyl)phenyl)acetylene anhydride,

1-phenyl-2-(4-(1,1,1,3,3,3-hexafluoro-2-(3,4-dicarboxyphenyl)isopropanyl)-phenyl)acetylene anhydride,

1-phenyl-2-(4-(3,4-dicarboxyphenyl)phenyl)acetylene anhydride, and

2,3-dicarboxy-6-phenylethynyl)naphthalene anhydride.

[0105] The above-described, crosslinkable-group-containing end blocking agents can be used either singly or in combination. End blocking agents in each of which some or all of the hydrogen atoms on one or more of the aromatic ring(s) have been replaced by a like number of substituent groups selected from fluoro groups, methyl groups, methoxy groups, trifluoromethyl groups and/or trifluoromethoxy groups can also be used.

[0106] Further, the above-described, crosslinkable-group-containing dicarboxylic acid anhydrides are also usable after in place of some or all of the hydrogen atoms on one or more of the aromatic ring(s) of each of the anhydrides, a like number of ethynyl group(s), benzocyclobuten-4'-yl group(s), vinyl group(s), allyl group (s), cyano group(s), isocyanate group(s), nitrilo group(s) and/or isopropenyl grsup (s), which can act as crosslinking points, are introduced as substituent group (s), preferably to an extent not impairing the moldability or formability.

[Most preferred, crosslinkable-group-containing end blocking agent]

[0107] Among the above-described, crosslinkable-group-containing end blocking agents, 1-phenyl-2-(3,4-dicarboxyphenyl acetylene anhydride is most preferred from the standpoint of the properties and practical application of the crosslinkable-group-cohtaining polyimide according to the present invention.

[Crosslinkable-group-free end blocking agent]

[0108] No limitation is imposed on the crosslinkable-group-free end blocking agent usable in the present invention. Depending on the synthesis process of the polyimide, a variety of crosslinkable-group-free end blocking agents can be used. Representative examples are monoamines or dicarboxylic acid anhydrides. It is essential that a group, which may function. as a crosslinking group under conditions of a molding or forming. step or post-treatment step, is not contained in the structure. Examples of the crosslinking group can include ethynyl group, benzocyclobuten-4'-yl group, vinyl group, allyl group, cyano group, isocyanate group, nitrilo group, amino group, isopropenyl group, vinylene group, vinylidene group, and ethynylidene group.

[Preferred, crosslinkable-group-free end blocking agents]

[0109] The crosslinkable-group-free end blocking agent usable in the present invention may preferably be a dicarboxylic acid anhydride. Depending on the synthesis process, its ring-opened product or its derivative such as its salt can be used.

[0110] Specific examples are:

phthalic anhydride,

4-phenylphthalic anhydride,

4-phenoxyphthalic anhydride,

4-phenylsulfinylphthallic acid,

4-phenylcarbonylphthalic acid,

4-(2-phenylisopropyl)phthalic anhydride,

4-(1,1,1,3,3,3-hexafluoro-2-phenylisopropyl)phthalic anhydride,

2,3-naphthalenedicarboxylic anhydride, and

1,8-naphthalenedicarboxylic anhydride.

[0111] The above-described dicarboxylic acid anhydrides can be used either singly or in combination. Diamines in each of which some or all of the hydrogen atoms on one or more of the aromatic ring(s) have been replaced by a like number of substituent groups selected from fluoro groups, methyl groups, methoxy groups, trifluoromethyl groups and/or trifluoromethoxy groups can also be used. [Most preferred, crosslinkable-group-free end blocking agent]

[0112] Among the above-described dicarboxylic acid anhydrides, phthalic acid is most preferred from the standpoint of the properties and practical application of the crosslinkable-group-containing polyimide according to the present invention.

[Molar ratio of the crosslinkable-group-containing end blocking agent to the crosslinkable-group-free end blocking agent]

[0113] No limitation is imposed on the molar ratio of the crosslinkable-group-containing blocking agent to the crosslinkable-group-free blocking agent insofar as the ends of the synthesized crosslinkable-group-containing polyimide satisfy the conditions that "the molecule ends have crosslinking groups at 1 to 80 mole % thereof". Preferably, however, their molar ratio falls within the following range:

where

[E1]:

the molar quantity of the used crosslinkable-group-containing blocking agent; and

[E2]:

the molar quantity of the used crosslinkable-group-free blocking agent ends.

[0114] If the value of [E1]/[E2] falls short of this range and is smaller than 1/99, no sufficient crosslinking density can be achieved, leading to insufficient improvements in chemical resistance, heat resistance and mechanical properties. If the value of [E1]/[E2] is greater than 80/20, on the other hand, a sufficient crosslinking density is available, but upon melt molding or forming, a substantial viscosity increase takes place so that the melt molding or forming becomes infeasible.

[0115] The range of the [E1]/[E2] value has to be chosen appropriately depending on molding or forming conditions. In general, however, the preferred range is:

and the more preferred range is:

[0116] The still more preferred range varies depending on the molding or forming process. For example, in a batchwise molding or forming process, such as compression molding, that involves residence in a molten state, the still more preferred range is:

and the most preferred range is:

[0117] For example, in a molding or forming process, such as injection molding or extrusion, that involves residence in a molten state and requires a continuous operation, the preferred range is:

and the most preferred range is:

[0118] For example, in a molding or forming process that does not involve much residence in a molten state, the preferred range is:

and the most preferred range is:

[Amount of the end blocking agent to be used]

[0119] No limitation is imposed on the amount of the end blocking agent to be used, insofar as the conditions that the ends of the synthesized crosslinkable-group-containing polyimide satisfy the conditions that "the molecule ends have crosslinking groups at 1 to 80 mole % thereof".

[0120] However, the end blocking agent may be used in an amount that satisfies preferably the following range:

more preferably the following range:

where

[Da]:

total amount of the diamine component (mol),

[Tc]:

total amount of the tetracarboxylic acid dianhydride component (or its ring-opened product or derivative) (mol),

[Ma]:

total amount of the monoamine component to be used as an end blocking agent (mol), and

[Dc]:

total amount of the dicarboxylic acid anhydride component (or its ring-opened product or derivative) to be used as an end blocking agent (mol).

If the value of ([Dc]-[Ma])/([Da]-[Tc]) falls short of this range and is smaller than it, no sufficient blocking of molecule ends is feasible, resulting in deteriorations in thermal stability, thermal oxidation stability, and moldability or formability. If the value exceeds the above range, on the other hand, it becomes difficult to control the molecular weight and also to wash off any extra portion of the end blockingagent.

[Production process of the crosslinkable-group-containing polyimide]

[0121] The polyimide can be obtained by providing the above-described raw materials and conducting polymerization and imidation by known methods. Although no limitation is imposed on the production process, the polymerization is generally conducted in a solvent.

[0122] Examples of the process can generally include:

A) a process which comprises stirring a diamine component and a tetracarboxylic acid dianhydride component in a solvent to obtain a crosslinkable-group-containing polyamic acid and then thermally or chemically conducting its dehydrating imidation, and

B) a direct polymerization process which comprises directly heating a diamine component and a tetracarboxylic acid dianhydride component, in a form dissolved or suspended in a solvent such that dehydrating imidation is thermally effected.

[Polymerization solvent].

[0123] Examples of the solvent can include:

m) Phenol solvents:
Phenol, o-chlorophenol, m-chlorophenol, p-chlorophenol; o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, and 3,5-xylenol;

n) Aprotonic amide solvents:
N,N-Dimethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidine, N-methylcaprolactam, and hexamethylphosphorotriamide;

o) Ether solvents:
1,2-Dimethoxyethane, bis(2-methoxyethyl) ether, 1,2-bis(2-methoxyethoxy)ethane, tetrahydrofuran, bis[2-(2-methoxyethoxy)ethyl] ether, and 1,4-dioxane;

p) Amine solvents:
Pyridine, quinoline, isoquinoline, α-picoline, β-picoline, γ-picoline, isophorone, piperidine, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, and tributylamine; and

q) Other solvents:
Dimethyl sulfoxide, dimethyl sulfone, diphenyl ether, sulphorane, diphenyl sulfone, tetramethylurea, anisole, and water.

[0124] These solvents can be used either singly or in combination. Each of these solvents can also be used by mixing it with one or more of solvents to be described subsequently herein under r), s), t) and u) . When used as a mixture, it is not absolutely necessary to choose solvents in such a combination that allows the solvents to be mutually dissolved at a desired ratio, and no problem or inconvenience arises even if they cannot be mixed or their mixture is not homogeneous.

[Polymerization concentration]

[0125] Absolutely no limitation is imposed on the concentration at which polymerization is to be conducted in such a solvent. Expressing the proportion of the total weight of the whole diamine component and the whole tetracarboxylic acid dianhydride component in terms of percentage on the basis of the total weight of the whole solvent, the whole diamine component and the whole tetracarboxylic acid dianhydride component, the preferred polymerization concentration is from 5 to 50%, with 10 to 30% being more preferred.

[Charging order]

[0126] No limitation is imposed on the order in which the diamine component, the tetracarboxylic acid dianhydride component and the end blocking agent are charged. when the diamine component, the tetracarboxylic acid dianhydride component or the end blocking agent consists of two or more kinds of diamines, dianhydrides or blocking agents, they can be added in an arbitrary order. It is also discretionary to add each component or agent at once or in portions.

[Polymerization conditions]

[0127] No particular limitation is imposed on the polymerization temperature, polymerization time or polymerization pressure. Known conditions can be applied.

[0128] The polymerization temperature may generally be in a range of from -10°C to 10°C in the case of the polymerization of the crosslinkable-group-containing polyamic acid, and is a range of from 50°C to 250°C in the case of the imidation. The reaction time may generally be from 1 to 48 hours, although it differs depending on the kinds of the monomers to be used, the kind of the solvent to be employed or the kind of the reaction temperature to be employed. Farther, as the reaction pressure, atmospheric pressure is sufficient.

[Logarithmic viscosity number of crosslinkable-group-containing polyamic acid]

[0129] When polymerization is conducted through a crosslinkable-group-containing polyamic acid, the logarithmic viscosity number of the crosslinkable-group-containing polyamic acid may preferably be in a range of from 0.1 to 2.0 dL/g (as measured at a concentration of 0.5 g/dL and 35°C in N,N-dimethylacetamide). A logarithmic viscosity number smaller than 0.1 leads to a decrease in the molecular weight between crosslinking points so that mechanical properties are lowered significantly, whereas a logarithmic viscosity number greater than 2.0 leads to an increase in melt viscosity so that melt moldability or formability is reduced substantially. The preferred logarithmic viscosity number is in a range of from 0.3 to 1.2, with a range of from 0.4 to 0.7 being more preferred.

[Chemical imidation]

[0130] Chemical imidation is a process to chemically effect dehydration by reacting the crosslinkable-group-containing polyamic acid with a dehydrating agent having hydrolytic ability.

[0131] Usable examples of the dehydrating agent can include aliphatic carboxylic acid anhydrides represented by acetic anhydride and trifluoroacetic anhydride; phosphoric acid anhydrides represented by polyphosphoric acid and phosphorus pentoxide; mixed acid anhydrides of these acids; and acid chlorides led by chloromethanesulfonic acid, phosphorus pentoxide and thionyl chloride. These dehydrating agents can be used either singly or in combination. These dehydrating agents can be used in an amount of 2 to 10 moles, preferably 2.1 to 4 moles, per mole of the whole amount of the diamine component to be used.

[0132] Further, chemical imidation can also be conducted in the presence of a base catalyst. As the base catalyst so used, the amine solvents mentioned above under p) can be mentioned. In addition, organic bases such as imidazole, N,N-dimethylaniline and N,N-diethylaniline as well as inorganic bases such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate and sodium hydrogencarbonate can be mentioned. These catalysts can be used in an amount of from 0.001 to 0.50 mole, preferably from 0.05 to 0.2 mole, per mole of the whole amount of the diamine component to be used.

[0133] No particular limitation is imposed on the reaction temperature, reaction time and reaction pressure for the chemical imidation process, and known conditions can be applied. Described specifically, the reaction temperature may preferably be from -10°C to around 120°C, with a range of from around room temperature to 70°C being more preferred. It is room temperature that is most preferable and practical from the standpoint of practice. On the other hand, the reaction time may preferably be from about 1 to 24 hours although it differs depending on the kind of the solvent to be used and other reaction conditions. More preferably, the reaction time may be from 2 to around 10 hours. As the reaction pressure, atmospheric pressure is sufficient. As the atmosphere, air, nitrogen, helium, neon or argon is usable, and no particular limitation is imposed thereon. Preferably, however, nitrogen or argon which is an inert gas is chosen.

[Thermal imidation]

[0134] Thermal imidation can be achieved by heating polyamic acid or its solution generally to 100°C to 300°C.

[0135] The thermal imidation can also conducted in the concurrent presence of a similar base catalyst as that employed in the chemical imidation process.

[0136] No particular limitation is imposed on the reaction temperature, reaction time and reaction pressure for the thermal imidation process, and known conditions can be applied. Described specifically, as the reaction temperature, 80°C to around 400°C can be used, with a range of from 100°C to around 300°C being preferred. On the other hand, the reaction time may preferably be from 0.5 to 24 hours although it differs depending on the kind of the solvent to be used and other reaction conditions. As the reaction pressure, atmospheric pressure is sufficient. As the atmosphere, air, nitrogen, helium, neon or argon is usable, and no particular limitation is imposed thereon. Preferably, however, nitrogen or argon which is an inert gas is chosen.

[Combined use of chemical imidation and thermal imidation]

[0137] Chemical imidation and thermal imidation can be used in combination.

[0138] Illustrative are:

A) a process in which heating is also conducted at the same time upon practice of the above-described chemical imidation process, and

B) a process in which upon conducting the above-described thermal imidation process, a dehydrating agent useful in chemical imidation is caused to exist concurrently.

[Direct polymerization process]

[0139] The term "direct polymerization process" as used herein means a process which comprises directly heating a diamine component and a tetracarboxylic acid dianhydride component in a form dissolved or suspended in a solvent such that dehydrating imidation is thermally effected. This direct polymerization is achieved by conducting polymerization and imidation in a solvent in a similar manner as in thermal imidation.

[0140] Like the chemical imidation process, the direct polymerization process can also be conducted in the concurrent presence of a base catalyst. Usable base catalysts and their amount to be used are the same as those described above in connection with the chemical imidation process.

[0141] Further, to take out of the system water which is to be formed by the dehydrating imidation reaction, it is also possible to make another solvent exist at the same time. Solvents which are usable here can include:
   r) benzene, toluene, o-xylene, m-xylene, p-xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, bromobenzene, o-dibromobenzene, m-dibromobenzene, p-dibromobenzene, o-chlorotoluene, m-chlorotoluene, p-chlorotoluene, o-bromotoluene, m-bromotoluene, and p-bromotoluene.

[0142] These solvents can be used either singly or in combination. Each of these solvents can also be used by further mixing it with one or more of the solvents described above under m) to q) and the solvents to be described subsequently under s) to u) . When used as a mixture, it is not absolutely necessary to choose solvents in such a combination that allows the solvents to be mutually dissolved at a desired ratio, and no problem or inconvenience arises even if they cannot be mixed or their mixture is not homogeneous. Absolutely no limitation is imposed on the amount of the dehydrating agent to be used.

[0143] No particular limitation is imposed on the reaction temperature, reaction time and reaction pressure, and known conditions can be applied. Described specifically, as the reaction temperature, 100°C to around 300°C can be applied, with a range of from 120°C to around 250°C being preferred. On the other hand, the reaction time may generally be from 0.5 hour to 24 hours although it differs depending on the kind of the solvent to be used and other reaction conditions. As the reaction pressure, atmospheric pressure is sufficient. As the atmosphere, air, nitrogen, helium, neon or argon is usable, and no particular limitation is imposed thereon. Preferably, however, nitrogen or argon which is an inert gas is chosen.

[Treatment of the crosslinkable-group-containing polyimide]

[0144] The crosslinkable-group-containing polyimide can be improved in chemical resistance, heat resistance, mechanical properties and the like by subjecting it to intermolecular crosslinking through its treatment during or after its molding or forming.

[0145] Conditions for such a crosslinking reaction are not. limited and can be set as desired. Further, these conditions significantly vary depending on the kind and quantity of crosslinkable groups to be used.

[0146] When crosslinkable-group-containing molecule ends are represented by the chemical formula (2a), for example, the preferred crosslinking method is heat treatment, and by the heat treatment, carbon-carbon triple bonds are thermally caused to react so that crosslinks are formed between molecular chains.

[Conditions for the heat treatment]

[0147] When crosslinkable-group-containing molecule ends are represented by the chemical formula (2a), the temperature, time and pressure of the heat treatment are not particularly limited, and are determined depending on properties required for a crosslinked thermoplastic polyimide to be obtained. As the temperature of the heat treatment, 250°C to around 450°C, preferably 300°C to around 400°C can be applied, with 330°C to around 380°C being most preferred from the standpoint of practice. At a temperature lower than 250°C the crosslinking reaction hardly takes, while at a temperature higher than 450°C, polyimide backbones undergo modifications so that their properties cannot be obtained sufficiently.

[0148] Although the time of the heat treatment differs depending on the other conditions for the heat treatment, it may be preferably 0.1 hour or longer, more preferably 0.2 hour or longer, and the most preferred, time is 1 hour or longer.

[0149] A heat treatment time shorter than this time results in an insufficient crosslinking density, thereby practically failing to observe improvements in physical properties.

[0150] On the other hand, an excessively long crosslinking time is disadvantageous from the standpoint of the process efficiency, and depending on the backbone structure, there is a potential problem of modifications. The upper limit of a preferred heat treatment time is 100 hours.

[0151] As the pressure for the heat treatment, atmospheric temperature is sufficient. If necessary, however, it is also possible to adopt such a process that heat treatment is effected while conducting degasfication or the like under elevated pressure.

[0152] As the atmosphere, air, nitrogen, helium, neon or argon is usable, and no particular limitation is imposed thereon. Preferably, however, nitrogen or argon which is an inert gas is chosen.

[Heat treatment method]

[0153] The heat treatment method differs depending on the form of a crosslinkable-group-containing polyimide, and no limitation is imposed thereon. When a crosslinkable-group-containing polyimide obtained, for example, in the form of powder or granules is used, examples of its heat treatment method can include:

A) to subject it, as is, to heat treatment;

B) to apply melt molding or forming to obtain a molded or formed product shaped as and then to subject the molded or formed product to heat treatment;

C) to simultaneously conduct heat treatment while applying melt molding or forming; and

D) to conduct its heat treatment, as is, to an intermediate extent, then to apply melt molding or forming to obtain a molded or formed product shaped as desired, and thereafter to subject the molded or formed product to heat treatment again.

[0154] As their applications, the followings are possible, respectively:

A) as a crosslinked thermoplastic polyimide is obtained in the form of powder or granules, it can be added, as is, as a filler to other resins or can be formed, as is, into a molded product by sinter molding;

B) all general melt molding or forming;

C) Forming of films or sheets especially by pressing, and their use as adhesives; and

D) All general melt molding or forming, especially forming of films or sheets by pressing and their use as adhesives.

[Treatment methods other than heat treatment]

[0155] Instead of heat treatment, various energy sources which induce crosslinking can be used. Illustrative are irradiations of visible light, ultraviolet rays, ultraviolet rays, radiations such as α-, β- and γ-rays, electron beams, and X-rays, and further, plasma treatment and doping treatment.

[Crosslinking promoter and crosslinking retarder]

[0156] A crosslinking promoter or crosslinking retarder can be used to control the crosslinking reaction velocity. No limitation is imposed on the crosslinking promoter or crosslinking retarder. A compound which, when used together with a crosslinkable-group-containing polyimide, can substantially promote or retard the crosslinking reaction, can be used in combination as desired.

[0157] It is possible to add, for example, a metal catalyst. containing gallium, germanium, indium or lead, a transition metal catalyst containing molybdenum, manganese, nickel, cadmium, cobalt, chromium, iron, copper, tin, platinum or the like, a phosphorus compound, a silicon compound, a nitrogen compound, or a sulfur compound.

[Solution or suspension containing a crosslinkable-group-containing polyimide]

[0158] A solution or suspension which contains a crosslinkable-group-containing polyimide according to the present invention can be used in a pre-treatment step of shaping or melt molding or forming of the crosslinkable-group-containing polyimide

[0159] The solution or suspension can be prepared using a solvent which does not cause a chemical reaction with the crosslinkable-group-containing polyimide according to the present invention.

[0160] Usable examples of the solvent can include, in addition to the solvent described above under m) to q) and r), the followings:

s) Acetone, methyl ethyl ketone, methyl isobutyl ketone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentane, hexane, heptane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, fluorobenzene, methyl acetate, ethyl acetate, butyl acetate, methyl formate, and ethyl formate;

t) Water, the amine solvents described above under p), imidazole, N,N-dimethylaniline, N,N-diethylaniline, and aqueous solutions containing potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogencarbonate, and sodium hydrogencarbonate, respectively; and

u) Silicone oil, machine oil, working oil, kerosine, gasoline, and jet fuel.

[0161] These solvents can be used either singly or in combination. They can also be used by further mixing them with one or more of the solvents described above under m) to r). When used as a mixture, it is not absolutely necessary to choose solvents in such a combination that allows the solvents to be mutually, dissolved at a desired ratio, and no problem or inconvenience arises even if they cannot be mixed or their mixture is not homogeneous. The concentrations of the aqueous solutions described above under t) are not limited and can be determined as desired. In general, their concentrations are in a range of from 1 to 60%.

[0162] No limitation is imposed on the preparation method of the solution or suspension which contains the polyimide according to the present invention, and all known methods are applicable.

[0163] Illustrative preparation methods can include:

A) to use, as is, a solution or suspension after completion of polymerization; and

B) to obtain the crosslinkable-group-containing polyimide in the form of powder, granules or a block, and then to dissolve or disperse it in the above-described solvent.

[0164] No limitations are imposed on the preparation conditions, such as temperature, time and stirring method, upon preparation of the solution or suspension. In the case of the suspension, no limitation is imposed on the particle size or particle size distribution of powder, granules or the like to be dispersed, and upon preparation, a dispersion promoter or an emulsifier can also be added.

[Alloys and blends with other resins]

[0165] In accordance with the application purpose of the crosslinkable-group-containing polyimide according to the present invention, it can be blended or alloyed, to an extent not impairing the object of the present invention, with suitable amount or amounts of one or more of resins such as thermoplastic resins, for example, polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polybutadiene, polystyrene, polyvinyl acetate ABS resin, polybutylene terephthalate, polyethylene terephthalate, polyphenylene oxide, polycarbonates, PTFE, celluloid, polyarylates, polyether nitriles, polyamides, polysulfones, polyether sulfones, polyether ketones, polyphenyl sulfide, polyamide-imides, polyether imides, modified polyphenylene oxide and polyimides, and thermosetting resins, for example, thermosetting polybutadiene, formaldehyde resins, amino resins, polyurethane, silicone resins, SBR, NBR, unsaturated polyesters, epoxy resins, polycyanates, phenol resins and polybismaleimide. No particular limitation is imposed on their blending or alloying method, and a known method can be applied.

[Fillers and additives]

[0166] With the crosslinkable-group-containing polyimide according to the present invention, various fillers or additives can be mixed to extents not impairing the object of the present invention. Their examples can include abrasion resistance improvers such as graphite, carborundum, silica powder, molybdenum disulfide and fluorinated resins; electrical characteristics improvers such as clay and mica; anti-track property improvers such as asbestos, silica and graphite; acid resistance improvers such as barium sulfate, silica and calcium metasilicate; thermal conductivity improvers such as iron powder, zinc powder, aluminum powder and copper powder; and further, glass beads, glass balls, talc, diatomaceous earth, alumina, Shirasu (white volcanic ash) balloons, alumina hydrate, metal oxides, colorants, and pigments. No particular limitation is imposed on the mixing method, and a known method can be applied.

Examples

[0167] The present invention will hereinafter be described in further detail by Examples. It should however be bone in mind that the present invention is by no means limited by the

Examples.

[0168] Testing methods of various tests, which are common to the Examples and Comparative Examples, are as described next:

1) Logarithmic viscosity number of polyimide powder
A sample (0.50 g) was dissolved under heat in 100 mL of a mixed solvent of p-chlorophenol and phenol (90:10 by weight ratio), and after cooling the solution. to 35°C, the logarithmic viscosity number was measured.

2) Melt viscosity
A melt viscosity was measured by a Shimadzu Koka-type flow tester ("CFT500A") through an orifice of 1.0 mm (diameter) x 10 mm (length), under a load of 100 kgf and, unless otherwise specifically indicated, under 360°C x 5 min.

3) 5% Weight loss temperature
Using DTA-TG ("Shimadzu DT-40 series, 40M"), a 5% weight loss temperature was measured at a heating rate of 10°C/min. in air.

4) Glass transition temperature and crystal melting temperature
Glass transition temperature and crystal melting temperature were measured at a heating rate of 10°C/min by DSC ("Shimadzu DT-40 series, DSC-41M").

5) Tensile strength of molded product
ASTM-D-638 was followed.

6) Logarithmic viscosity number of polyamic acid varnish
After a varnish the solid content of which was 0.50 g was dissolved in N-methyl-2-pyrrolidone to give a total volume of 100 mL, its logarithmic viscosity number was measured at 35°C.

7) Mechanical properties of film
Mechanical properties were measured following ASTM D-822.

8) Heat distortion temperature
ASTM D-648 was followed.

Experiment A Series

[0169] In Example A1 to Example A91, a description will be made about certain examples out of the present invention, in each of which 50 to 100 mole % of recurring structural units in a backbone structure are of a recurring unit structure represented by:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group; and
R represents a tetravalent aromatic group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group.

Examples A1-A7, Comparative Examples A1-A3

[0170] In each of these examples and comparative examples, 4,4'-bis(3-aminophenoxy)biphenyl (368.43 g, 1.000 mol), pyromellitic dianhydride (102.52 g, 0.470 mol), and 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (138.28g, 0.470 mol) were charged as monomers together with the corresponding end blocking agent (s), the kind(s) and amount(s) of which are shown in Table A1, and m-cresol (1,830 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and reactions were conducted under 200°C reflux conditions for 4 hours.

Table A1

Ex./Comp.Ex. No.	Charged amount of PA		Charged amount of PCE		PA/PCE molar ratio
	[g]	[mmol]	[g]	[mmol]
Example A1	17.60	118.8	0.2979	1.200	99/1
Example A2	16.89	114.0	1.489	6.000	95/5
Example. A3	16.00	108.8	2.979	12.00	90/10
Example A4	14.22	96.00	5.958	24.00	80/20
Example A5	10.66	72.00	11.92	48.00	60/40
Example A6	7.110	48.00	17.87	72.00	40/60
Example A7	3.555	24.00	23.83	96.00	20/80
Comp.Ex. A1	2.666	18.00	25.32	102.0	15/85
Comp. Ex. A2	0	0	29.79	120.0	0/100
Comp.Ex. A3	17.77	120.0	0	0	100/0
[Note] In Table A1, "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride.

[0171] The temperature was then lowered to 190°C, at which the corresponding end blocking agent(s) shown in Table A1 were charged again. The resulting contents were heated again, and the reactions were then conducted under 200°C reflux conditions for further 4 hours.

[0172] The reaction mixture was thereafter cooled to 100°C, the resulting viscous polymer solution was discharged into toluene (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in toluene (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 220°C for 12 hours under a nitrogen gas stream. The yield of the thus-obtained powder and the logarithmic viscosity number, glass transition temperature; 5% weight loss temperature and melt viscosity (360°C/5 min.) are shown in Table A2.

[0173] The present invention is characterized in that concerning the molecule ends, the ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is also evident that those having ratios of the chemical formula (2a) to the chemical formula (2b) greater than 80/20 are considerably inferior in moldability or formability to those having ratios of the chemical formula (2a) to the chemical formula (2b) equal to or smaller than 80/20.

Examples A8-A12, Comparative Examples A4,A5.

[0174] Using the powders obtained in Examples A2-A6 and Comparative Example 3, compression molding was conducted. The powders used in the respective examples and comparative examples are shown next in Table A3.

Table A3

Ex./Comp.Ex. No.	Ex./Comp.Ex. No. of used powder
Example A8	Example A2
Example A9	Example A3
Example A10	Example A4
Example A11	Example A5
Example A12	Example A6
Comp.Ex. A4, A5	Comp.Ex. A3

[0175] Described specifically, in each of these examples and comparative examples, the powder was extruded into pellets at 355°C by a 25-mm single-screw extruder. After the pellets were filled in a compression mold of configurations specified in ASTM-D-638, compression molding was conducted at 360°C for 12 hours (Examples A8-A12, Comparative Example A4) or under conditions of 360°C and 5 minutes (Comparative Example A5). In all the examples and comparative examples, good molded products were obtained. Using those molded products, a tensile test was performed at room temperature (23°C). The results are shown in Table A4.

[0176] The present invention is characterized in that concerning the molecule ends, the ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is also evident that those having ratios of the chemical formula (2a) to the chemical formula (2b) not reaching 1/99 are inferior in mechanical properties to those having ratios of the chemical formula (2a) to the chemical formula (2b) equal to or greater than 1/99.

Examples A13-A17, Comparative Examples A6-A8

[0177] In each of these examples and comparative examples, 4,4'-bis(3-aminophenoxy)biphenyl (368.43 g, 1.000 mol), pyromellitic dianhydride (102.52 g, 0.470 mol), and 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (138.28g, 0.470 mol) were charged as monomers together with m-cresol (1, 630 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 200°C over 2 hours and 30 minutes, under a nitrogen atmosphere, and a reaction was conducted under 200°C reflux conditions for 2 hours, whereby a solution of an end-unblocked polymer was obtained. During the reaction, the corresponding end blocking agent(s) described in Table A5 and m-cresol (200.0 mL) were charged into another vessel and were then heated beforehand at 100°C for 1 hour under a nitrogen atmosphere to provide a solution. The solution of the end blocking agent(s) was charged in its entirety into the solution of the end-unblocked polymer, and reaction(s) was(were) then conducted under 200°C reflux conditions for 2 hours.

Table A5

Ex./Comp.Ex. No.	Charged amount of PA		Charged amount of PCE		PA/PCE molar ratio
	[g]	[mmol]	[g]	[mmol
Example A13	33.77	228.0	2.979	12.0	95/5
Example A14	31.99	216.0	5.958	24.0	90/10
Example A15	28.44	192.0	11.96	48.0	80/20
Example A16	21.33	144.0	23.83	96.0	60/40
Example A17	14.21	96.00	35.75	144.0	40/60
Comp.Ex. A6	5.332	36.00	50.64	204.0	15/85
Comp.Ex. A7	0	0	59.58	240.0	0/100
Comp.Ex. A8	35.55	240.0	0	0	100/0
[Note] In Table A5, "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride.

[0178] The reaction mixture was thereafter cooled to 100°C. While maintaining the resultant viscous polymer solution at 100°C, toluene (4 liters) was charged dropwise into the polymer solution over 4 hours. After toluene (3 liters) which had been heated at 80°C was additionally charged, the resulting mixture was allowed to cool down to room temperature. Toluene (3 liters) was added further, followed by stirring for 1 hour. A precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in toluene (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 200°C under reduced pressure for 12 hours under a gentle nitrogen gas stream. The yield of the thus-obtained powder and the logarithmic viscosity number, glass transition temperature, 5% weight loss temperature and melt viscosity (360°C/5 min.) are shown in Table A6.

[0179] The present invention is characterized in that concerning the molecule ends, the ratio of the chemical, formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is also evident that those having ratios of the chemical formula (2a) to the chemical formula (2b) greater than 80/20 are considerably inferior in moldability or formability to those having ratios of the chemical formula (2a) to the chemical formula (2b) equal to or smaller than 80/20.

Examples A18-A22, Comparative Examples A9, A10.

[0180] Using the powders obtained in Examples A13-A17 and Comparative Example A8, compression molding was conducted. The powders used in the respective examples and comparative examples are shown next in Table A7.

Table A7

Ex./Comp.Ex. No.	Ex./Comp.Ex. No. of used powder
Example A18	Example A13
Example A19	Example A14
Example A20	Example A15
Example A21	Example A16
Example A22	Example A17
Comp.Ex. A9,A10	Comp.Ex. A8

[0181] Described specifically, in each of these examples and comparative examples, the powder was extruded into pellets at 355°C by a 25-mm single-screw extruder. After the pellets were filled in a compression mold having a size of 10.0 mm in width and 80.0 mm in length, compression molding was conducted at 360°C for 12 hours (Examples A18-A22, Comparative Example A9) or under conditions of 360°C and 5 minutes (Comparative Example A10). In all the examples and comparative examples, good molded products were obtained. Those specimens were all of 10.0 mm ± 0.010 mm in width, 80.0 mm ±0.010 mm in length and 1.500 mm ± 0.010 mm in thickness. Using those molded products, a chemical resistance test was performed by the below-described method.

[0182] Described specifically, each specimen was held in place at portions 5.00 mm apart from opposite ends thereof, and was then adjusted and fixed such that a displacement of 3.50 mm in the direction of the thickness would be given when the specimen was bent by a jig maintained in contact with the specimen at a center thereof (a portion 40.0 mm apart from the respective ends). Under those conditions, the specimen was immersed in toluene or methyl ethyl ketone. One hour, 24 hours and 168 hours later, the specimen caas taken out of the solvent and visually observed for cracks. The results of the chemical resistance test are shown in Table A8.

[0183] The present invention is characterized in that concerning the molecule ends, the ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is evident that those having ratios of the chemical formula (2a) to the chemical formula (2b) not reaching 1/99 are inferior in chemical resistance to those having ratios of the chemical formula (2a) to the chemical formula (2b) equal to or greater than 1/99.

Table A8

Ex./Comp.Ex. No.	Toluene immersion time			MEK immersion time			PA/PCE molar ratio
	1hr.	24hr.	168hr.	1hr.	24hr.	168hr.
Example A18	A	A	A	B	B	C	95/5
Example A19	A	A	A	A	B	B	90/10
Example A20	A	A	A	A	A	B	80/20
Example A21	A	A	A	A	A	A	60/40
Example A22	A	A	A	A	A	A	40/60
Comp.Ex.A9	A	B	B	C	C	C	0/100
Comp.Ex.A10	A	B	B	C	C	C	0/100
[Note] In Table A8, "A", "B" and "C" indicate "completely free of cracks", "cracks observed in a very small number" and "cracks observed in a large number", respectively, in this order. Further,' "PA/PCE molar ratio" means the molar ratio of phthalic anhydride to 1-phenyl-2-(3,4-dicarboxy-phenyl)acetylene anhydride, and "MEK" stands for methyl ethyl ketone.

Examples A23-A32, Comparative Examples A11-A16

[0184] In each of these examples and comparative examples, the following two reactions (A),(B) were conducted.

(A) 4,4'-Bis(3-aminophenoxy)biphenyl (368.43 g, 1.000 mol), pyromellitic dianhydride (102.52 g, 0.470 mol), and 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (138.28 g, 0.470 mol) were charged as monomers together with phthalic anhydride (10.66 72.00 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (11.92 g, 48.00 mmol) as end blocking agents, m-cresol (1,830 g) as a solvent, and γ -picoline (13.970 g, 0.1500 mol) as a catalyst into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 150°C over 2 hours under a nitrogen atmosphere, and reactions were conducted at 150°C for 2 hours.
As end blocking agents, phthalic anhydride (5.33 g, 36.00 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (5.96 g, 24.00 mmol) were then charged, followed by the reactions at 150°C for further 8 hours.
The reaction mixture was thereafter cooled to 60°C, the resulting viscous polymer solution was discharged into methyl ethyl ketone (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in methyl ethyl ketone (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 220°C for 12 hours nder a nitrogen gas stream, whereby polyimide powder was obtained.

(B) In each of these examples and comparative examples, polyimide powder was obtained in exactly the same manner as in the reaction (A) except that upon preparation of the make-up, the amount(s) of the end blocking agent(s) of the kind(s) was (were) changed to only phthalic anhydride (17.77 g, 120.00 mmol) and that during the reactions, the amount (s) of the end blocking agent(s) of the kind(s) was(were) changed to only phthalic anhydride (8.89 g, 60.00 mmol).

[0185] The yields, of the powders obtained in the two reactions (A), (B) and their logarithmic viscosity numbers, glass transition temperatures, 5% weight loss temperatures and melt viscosities (360°C/5 min.) are shown in Table A9.

[0186] Further, each powder was extruded into pellets at 355°C by a 25-mm single-screw extruder. After the pellets were filled in a compression mold of the shape specified in ASTM-D-638, compression molding was conducted under the conditions described in Table A10.

Table A10

Ex./Comp.Ex. No.	Used powder	Compression molding conditions
Examples A23,A28	(A)	360°C, 2 hr.
Examples A24,A29	(A)	360°C, 6 hr.
Examples A25,A30	(A)	360°C, 12 hr.
Examples A26, A31	(A)	360°C, 24 hr.
Examples A27,A32	(A)	360°C, 72 hr.
Comp.Ex. A11, A14	(B)	360°C, 2 hr.
Comp.Ex. A12,A15	(B)	360°C, 12 hr.
Comp.Ex. A13,A16	(B)	360°C, 72 hr.

[0187] Using the specimens so obtained, a tensile test at room temperature (23°C) and a high-temperature tensile test at 177°C were performed. The results are shown in Table A11.

[0188] From the foregoing, it is evident that the crosslinkable-group-containing polyimide according to the present invention can be significantly improved in roomtemperature and high-temperature mechanical properties by annealing, and it is also appreciated that this effect cannot be expected from the conventional polyimides of the comparative examples.

Examples A28-A32, Comparative Examples A14-A16

[0189] In each of these examples and comparative examples, pyromellitic dianhydride and 3,3',4,4'-biphenyl-tetracarboxylic acid dianhydride were charged in their corresponding amounts shown in Table A12 together with 4,4'-bis(3-aminophenoxy)biphenyl (368.43 g, 1.000 mot), all as monomers, into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. As a solvent, m-cresol was also charged in its corresponding amount shown in Table A12. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and a reaction was conducted under 200°C reflux conditions for 2 hours, whereby a solution of an end-unblocked polymer was obtained.

[0190] During the reaction, the corresponding end blocking agents described in Table A13 and m-cresol (200.0 mL) were charged into another vessel and were then heated beforehand at 100°C for 1 hour under a nitrogen atmosphere to provide a solution. The solution of the end blocking agents was charged in its entirety into the solution of the end-unblocked polymer, and reactions were then conducted under 200°C reflux conditions for 2 hours.

Table A12

Ex./Comp.Ex. No.	Charged amount of PMDA		Charged amount of BPDA		Charged amount of m-cresol [g]
	[g]	[mol]	[g]	[mol]
Example A28	146.58	0.6720	84.74	0.2880	1600
Example A29,31	142.00	0.6510	82.09	0.2790	1580
Example A30,32	137.42	0.6300	79.44	0.2700	1560
Comp.Ex.A14	146.58	0.6720	84.74	0.2880	1600
Comp.Ex.A15	142.00	0.6510	82.09	0.2790	1580
Comp.Ex.A16	137.42	0.6300	79.44	0.2700	1560
[Note] In Table A12, "PMDA" stands for pyromellitic dianhydride, and "BPDA" stands for 3,3',4,4'-biphenyl-tetracarboxylic acid dianhydride.

Table A13

Ex./Comp.Ex. No.	Charged amount of PA		Charged amount of PCE		PA/PCE molar ratio
	[g]	[mmol]	[g]	[mmol]
Example A28	16.59	112.0	11.92	48.00	70/30
Example A29	29.03	196.0	20.85	84.00	70/30
Example A30	41.47	280.0	29.79	120.0	70/30
Example A31	20.74	140.0	34.75	140.0	50/50
Example A32	29.62	200.0	49.45	200.0	50/50
Comp.Ex. A14	3.555	24.00	33.76	136.0	15/85
Comp.Ex. A15	6.221	42.00	59.08	238.0	15/85
Comp.Ex. A16	8.887	60.00	84.40	340.0	15/85
[Note] In Table A13, "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride.

[0191] The reaction mixture was thereafter cooled to 60°C, the resulting viscous polymer solution was discharged into methyl ethyl ketone (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in methylethyl ketone (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 220°C for 12 hours. under a nitrogen gas stream, whereby polyimide powder was obtained.

[0192] The logarithmic viscosity number, glass transition temperature, 5% weight loss temperature and melt viscosity (360°C/5 mim., 15 min., 30 min.) of the thus-obtained polyimide powder are shown in Table A14.

[0193] It is appreciated from the results that the crosslinkable-group-containing polyimide according to the present invention, even at various molecular weights, has good melt fluidity and is better in moldability or formability than the polyimides of the comparative examples.

Examples A33-A37, Comparative Examples A17-A19

[0194] In each of these examples and comparative examples, pyromellitic dianhydride and N-methyl-2-pyrrolidone were charged in their corresponding amounts shown in Table A15 together with 4,4'-bis(3-aminophenoxy)biphenyl (368.43 g, 1.000 mol) into a vessel equipped with a stirrer and a nitrogen gas inlet tube. While stirring the contents under a nitrogen atmosphere, a reaction was conducted at room temperature for 12 hours, whereby a polyamic acid varnish was obtained. The corresponding end blocking agents, the kind(s) and amount(s) of which are shown in Table A15, were charged into the thus-obtained varnish, followed by reactions at room temperature for 12 hours.

[0195] The logarithmic viscosity number of the thus-obtained polyamic acid varnish is shown in Table A16. Using that varnish, a film was prepared. Described specifically, the varnish was evenly cast on a soft glass plate. Within an oven through which a nitrogen gas stream was flowing, the film was heated from 50°C. to 200°C at a heating rate of 1°C per minute, and was then cured at 200°C for 2 hours. Further, the film was heated from 200°C to 370°C at a heating rate of 15°C per minute, and was then annealed at 370°C for 4 hours. After the resulting film was quenched, hot water was poured over the film such that the film was peeled off from the glass plate. Incidentally, the film of Comparative Example A19 was so brittle that upon quenching, it shattered into small pieces, thereby failing to obtain a film. From the films of the remaining examples, good films were obtained. A tensile test of each film, which had been obtained by the above-described procedures, was performed at room temperature (23°C). The results are shown in Table A16.

[0196] From these results, it is evident that the crosslinkable-group-containing polyimide according to the present invention, at various molecular weights, exhibits better physical properties than the polyimides of the comparative examples.

Examples A38-A42, Comparative Examples A20-A22

[0197] In each of these examples and comparative examples, 500 mL of the corresponding one of the varnishes - which had been obtained in Examples A33-A37 and Comparative Examples A17-A19, respectively - were discharged into methanol (10 liters) which was under vigorous agitation, and a precipitate was collected by filtration. The precipitate was washed further with methanol (800 mL). After provisional drying under reduced pressure at 50°C for 24 hours, the precipitate was dehydrated and imidated under reduced pressure at 250°C for 12 hours under a gentle nitrogen gas stream, whereby polyimide powder was obtained. The used varnish and the glass transition temperature and 5% weight loss temperature of the thus-obtained polyimide powder are shown in Table A17.

[0198] Further, the powder was placed on a heat-resistant dish, annealed under nitrogen gas at 380°C for 2 hours, and then quenched. Thereafter, its glass transition temperature and 5% weight loss temperature were measured. The results are shown in Table A17.

[0199] From these results, it is appreciated that, when annealed, the crosslinkable-group-containing polyimide according to the present invention is significantly improved in glass transition temperature but the polyimides of the comparative examples are not improved.

Table A17

Ex./Comp.Ex. No..	Used varnish	Before annealing		After annealing
		Tg[°C],	Td5[°C]	Tg[°C],	Td5[°C]
Example A38	Example A33	245	560	268	552
Example A39	Example A34	245	560	266	553
Example A40	Example A35	244	559	265	554
Example A41	Example A36	242	552	264	550
Example A42	Example A37	237	544	265	543
Comp.Ex.A20	Comp.Ex.A17	245	561	244	555
Comp.Ex.A21	Comp.Ex.A18	244	560	243	554
Comp.Ex.A22	Comp.Ex.A19	235	542	235	521
[Note] In Table A17, "Tg" indicates a glass transition temperature, and "Td5" designates a 5% weight loss temperature.

Examples A43-A45, Comparative Example A23

[0200] In each of these examples and comparative example, 4,4'-bis(3-aminophenoxy)biphenyl (368.43 g, 1.000 mol) and pyromellitic dianhydride (205.03 g, 0.940 mol) were charged as monomers together with m-cresol (1,520 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and a reaction was conducted under 200°C reflux conditions for 2 hours, whereby a solution of an end-unblocked polymer was obtained. During the reaction, the corresponding end blocking agent (s) described in Table A18 and m-cresol (200.0 mL) were charged into another vessel and were then heated beforehand at 100°C for 1 hour under a nitrogen atmosphere to provide a solution. The solution of the end blocking agent(s) was charged in its entirety into the solution of the end-unblocked polymer, and reaction(s) was(were) then conducted under 200°C reflux conditions for 2 hours.

Table A18

Ex./Comp.Ex. No.	Charged amount of PA		Charged amount of PCE		PA/PCE molar ratio
	[g]	[mmol]	[g]	[mmol]
Example A43	33.77	228.0	2.979	12.0	95/5
Example A44	31.99	216.0	5.958	24.0	90/10
Example A45	28.44	192.0	11.92	48.0	80/20
Comp.Ex. A23	17.77	120.0	0	0	100/0
[Note] In Table A18, "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride.

[0201] The reaction mixture was thereafter cooled to 100°C. While maintaining the resultant viscous polymer solution at 100°C, toluene (4 liters) was charged dropwise into the polymer solution over 4 hours. After toluene (3 liters) which had been heated at 80°C was additionally charged, the resulting mixture was allowed, to cool down to room temperature. Toluene (3 liters) was added further, followed by stirring for 1 hour. A precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in toluene (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 200°C under reduced pressure for 12 hours under a gentle nitrogen gas stream. The logarithmic viscosity number, glass transition temperature, crystal melting temperature, 5% weight loss temperature and melt viscosity (410°C/5 min.) of the thus-obtained polyimide powder are shown in Table A19.

[0202] Using the polyimide powder so obtained, pelletization was conducted at 400°C by extrusion. Injection molding was then conducted at a resin temperature o.f from 380 to 410°C, an injection pressure of from 1,400 to 1,600 kg/cm² and a mold temperature of 170°C, whereby an amorphous specimen of the shape specified in ASTM-D-638 was obtained.

[0203] To the thus-obtained amorphous specimen, annealing treatment was applied further under a nitrogen gas stream, whereby the specimen was crystallized and, where the specimen was that of one of the examples, the specimen was subjected to crosslinking. The annealing treatment consisted of the following nine steps: ① heating from room temperature to 220°C at a heating rate of 5°C/min., ② annealing at 220°C for 5 hours, ③ heating from 220°C to 280°C at a heating rate of 5°C/min., ④ annealing at 280°C for 5 hours, ⑤ heating from 280°C to 320°C at a heating rate of 5°C/min., ⑥ annealing at 320°C for 5 hours, ⑦ heating from 320°C to 350°C at a heating rate of 5°C/min., ⑧ annealing at 350°C for 24 hours, and ⑨ cooling to room temperature at a cooling rate of 5°C/min.

[0204] Using the specimen, a tensile test was performed. The results are shown in Table A20.

[0205] From the above results, it is evident that the crosslinkable-group-containing polyimide according to the present invention, even when crystallized, has good mechanical properties.

Examples A46-A49, Comparative Examples A24-A27

[0206] In each of these examples and comparative examples, the following two reactions (A), (B) were conducted.

(A) 4,4'-Bis(3-aminophenoxy)biphenyl (368.43 g, 1.000 mol), pyromellitic dianhydride (101.43 g, 0.465 mol) and 3,3',4,4'-biphenyltetracarboxylicacid anhydride (136.81 g, 0.465 mol) were charged as monomers together with m-cresol (1,820 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 200°C over 3 hours under a nitrogen atmosphere, and a reaction was conducted under 200°C reflux conditions for 2 hours, whereby a solution of an end-unblocked polymer was obtained. During the reaction, phthalic anhydride (20.74 g, 140.0 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (34.75 g, 140.0 mmol) were charged as end blocking agents together with m-cresol (200.0 mL) into another vessel, and were then heated beforehand at 100°C for 1 hour under a nitrogen atmosphere to provide a solution. The solution of the end blocking agents was charged in its entirety into the solution of the end-unblocked polymer, and reactions were then conducted under 200°C reflux conditions for 2 hours.
The reaction mixture was thereafter cooled to 60°C, the resulting viscous polymer solution was discharged into methanol (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in methanol (4 liters). After the reprecipitate was collected, by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 220°C for 12 hours under a nitrogen gas stream, whereby polyimide powder was obtained.

(B) In each of these examples and comparative examples, polyimide powder was obtained in exactly the same manner as in the reaction (A) except that the amounts of the end blocking agents of the kinds were changed to only phthalic anhydride (41.47 g, 280.00 mmol).

[0207] The logarithmic viscosity numbers, glass transition temperatures, 5% weight loss temperatures and melt viscosities (360°C/5 min.) of the powders obtained in the two reactions (A), (B) are shown in Table A21.

[0208] Further, each powder was extruded into pellets at 355°C by a 25-mm single-screw extruder. After the pellets were filled in a compression mold of the shape specified in ASTM-D-638, compression molding was conducted under the conditions described in Table A22.

[0209] Using the thus-obtained specimen, a chemical resistance test was performed. Described specifically, the specimen was fixed on a jig in a state stretched by 0.5%, and was then immersed in toluene or methyl ethyl ketone at room temperature (23°C) for 24 hours. Using the immersed specimen, a tensile test was performed at room temperature (23°C). The results of the tensile test were compared with those of a tensile test of a corresponding non-immersed specimen, and a break strength retention (%) was calculated. The term "break strength retention (%)" as used herein means a value expressed in terms of percentage by comparing the break strength of an immersed specimen with the break strength of a corresponding non-immersed specimen.

[0210] The results are shown in Table A22.

[0211] From the above results, it is evident that the crosslinkable-group-containing polyimide according to the present invention is significantly improved in chemical resistance by annealing under various conditions irrespective of the annealing temperature. It is appreciated that this effect cannot be expected from the conventional polyimides of the comparative examples.

Examples A50-A54, Comparative Examples A28-A32

[0212] In each of these examples and comparative examples, polyimide powder was synthesized in exactly the same manner as in Examples A13-A17 except that the corresponding one of various diamines and pyromellitic dianhydride (202.85 g, 0.930 mol) were used as monomers and that phthalic anhydride (20.74 g, 140.0 mmol) and 1-phenyl-2-(3,4-dicarboxy-phenyl)acetylene anhydride (34.75 g, 140.0 mmol) were used as end blocking agents in each of the examples but only phthalic anhydride (41.47 g, 280.00 mmol) was used as an end blocking agent in each of the comparative examples.

[0213] Further, the thus-obtained polyimide powder was extruded into pellets at 325°C to 365°C by a 25-mm single-screw extruder. After the pellets were filled in a compression mold of the shape specified in ASTM-D-648, Compression molding was conducted under the conditions of 360°C and 6 hours.

[0214] Using the specimen so obtained, its heat distortion temperature was measured.

[0215] The kinds and amounts of the diamines, which were used in the respective examples and comparative examples, and the heat distortion temperatures are shown in Table A23.

Examples A55-A59, Comparative Examples A33-A37

[0216] In each of these examples and comparative examples, polyimide powder was synthesized in exactly the same manner as in Examples A13-A17 except that the corresponding one of various diamines, 4,4'-bis(3-aminophenoxy)biphenyl (331.59 g, 0.900 mol) arid pyromellitic dianhydride (202.85 g, 0.930 mol) were used as monomers and that phthalic anhydride (20.74 g, 140.0 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)-acetylene anhydride (34.75g, 140.0 mmol) were used as end blocking agents in each of the examples but only phthalic anhydride (41.47 g, 280.00 mmol) was used as an end blocking agent in each of the comparative examples.

[0217] In a similar manner as in Examples A50-A54, specimens were then obtained from the respective polyimide powders, and their heat distortion temperatures were measured. The kinds and amounts of the diamines, which were used in the respective examples, and the heat distortion temperatures are shown in Table A24.

Examples A60-A64, Comparative Examples A38-A42

[0218] In each of these examples and comparative examples, polyimide powder was synthesized in exactly the same manner as in Examples A13-A17 except that the corresponding ones of various diamines, 4,4'-bis(3-aminophenoxyl)biphenyl (221.058 g, 0.600 mol) and pyromellitic dianhydride (202.85 g, 0.930 mol) were used as monomers and that phthalic anhydride (20.74 g, 140.0 and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (34.75 g, 140.0 mmol) were used as end blocking agents in each of the examples but only phthalic anhydride (41.47 g, 280.00 mmol) was used as an end blocking agent in each of the comparative examples.

[0219] In a similar manner as in Examples A50-A54, specimens were then obtained, and their heat distortion temperatures were measured.

[0220] The kinds and amounts of the diamines, which were used in the respective examples and comparative examplds, and the heat distortion temperatures are shown in Table A25.

Examples A65-A69, Comparative Examples A43-A47

[0221] In each of these examples and comparative examples, polyimide powder was synthesized in exactly the same manner as in Examples A13-A17 except that 4,4'-bis(3-aminophenoxy)biphenyl (368.43 g; 1.000 mol) and the corresponding one of various acid anhydrides were used as monomers and that phthalic anhydride (20.74 g, 140.0 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (34.75 g, 140.0 mmol) were used as end blocking agents in each of the examples but only phthalic anhydride (41.47 g, 280.00 mmol) was used as an end blocking agent in each of the comparative examples. In a similar manner as in Examples A50-A54, specimens were then obtained, and their heat distortion temperatures were measured.

[0222] The kinds and amounts of the acid anhydrides, which were used in the respective examples and comparative examples, and the heat distortion temperatures are shown in Table A26.

[0223] From the above test, it is evident that crosslinkable-group-containing polyimides according to the present invention, which have various structures, are far superior in heat resistance to similar polymers having no crosslinkable groups.

Examples A70-A75, Comparative Examples A43-A48

[0224] In each of these examples and comparative examples, a 15% (W/W) polyamic acid varnish was obtained in a similar manner as in Examples A33-A37 by using dimethyl acetamide as a solvent, the corresponding diamine(s) and acid anhydride (s), the amounts and kinds of which are shown in Table A27, as monomers, and phthalic anhydride (10.66 g, 72.00 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (11.92 g, 48.00 mmol) as end blocking agents in each of the examples or only phthalic anhydride (17.77 g, 120.00 mmol) as an end blocking agent in each of the comparative examples.

[0225] Using the thus-obtained varnishes, films were prepared under similar conditions as in Examples 33-37. Those films were punched by a die, whereby elongated rectangular specimens of 5.00 mm in width and 260 mm in length were obtained. Using those specimens, a chemical resistance test was performed.

[0226] Described specifically, each film was held in place at portions 5.00 mm apart from opposite ends thereof. Using a device capable of finely adjusting the distance between those portions, the distance between those portions was set at 251.75 mm. Under those conditions, the specimen was immersed together with the device in toluene or methyl ethyl ketone. One hour, 24 hours and 168 hours later, the specimen was taken out of the solvent and visually observed for cracks. The results are shown together with the logarithmic viscosity numbers of the varnishes in Table A28.

[0227] Incidentally, "A", "B" and "C" in Table A28 indicate "completely free of cracks", "cracks observed in a very small number" and "cracks observed in a large number", respectively, in this order. Further, "MEK" stands for methyl ethyl ketone.

Table A28

Ex./Comp. Ex. No.	Logarithmic viscosity number [dL/g]	Toluene immersion time			MEK immersion time
		1hr.	24hr.	168hr.	1hr.	24hr..	168hr.
Example A70	0.455	A	A	A	A	A	A
Example A71	0.461	A	A	A	A	A	A
Example A72	0.449	A	A	A	A	A	B
Example A73	0.466	A	A	A	A	A	B
Example A74	0.480	A	A	A	A	A	A
Example A75	0.452	A.	A	A	A	A	A
Comp.Ex.A48	0.449	A	B	B	B	C	C
Comp.Ex.A49	0.466	A	B	B	B	C	C
Comp.Ex.A50	0.453	A	B	B	C	C	C
Comp.Ex.A51	0.470	A	B	B	C	C	C
Comp.Ex.A52	0.478	A	B	B	B	C	C
Comp.Ex.A53	0.451	A	A	B	B	B	C

Examples A76-A79, Comparative Example A54

[0228] In each of these examples and comparative example, a 15% (W/W) polyamic acid varnish was obtained in a similar manner as in Examples A33-A37 by using dimethylformamide as a solvent and 4,4'-bis(3-aminophenoxy)biphenyl (368.43 g, 1.000 mol) and pyromellitic dianhydride (142.00 g, 0.651 mol) and 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (89.90 g, 0.279 mol) as monomers together with the corresponding end blocking agent(s) the amount(s) and kind(s) of which are shown in Table A29.

[0229] Using the thus-obtained varnishes, films were prepared under similar conditions as in Examples 33-37. Employing those films, a chemical resistance test was performed in toluene in a similar manner as in Examples A70-A75. The results are shown together with the logarithmic viscosity numbers of the varnishes in Table A29.

[0230] Incidentally, "A", "B" and "C" in Table A28 indicate "completely free of cracks", "cracks observed in a very small number" and "cracks observed in a large number", respectively, in this order.

[0231] From the above results, it is evident that crosslinkable-group-containing polyimides according to the present invention, which have various structures, are far superior in heat resistance to similar polymers having no crosslinkable groups.

Examples A80-A82

[0232] Using the polyimide powders employed above in Examples A28-A30, their melt viscosities were measured by varying the measuring temperature and the residence time in various ways within a range of from 300°C to 400°C. The results are shown in Table A30.

[0233] Incidentally, the shearing stress under those measuring conditions was constant at 0.245 MPa.

Table A30

Ex. No.	Ex. No. of used powder	Measuring temp. [°C]	Melt viscosity[Pa·S]
			5min.	30min.
Example A80	Example A28	300	No flow	←
		320	58000	59200
		340	10800	11500
		360	3280	4120
		380	1650	7820
		400	1770	18000
Example A81	Example A29	300	No flow	←
		320	115.00	11600
		340	2110	2300
		360	890	1130
		380	510	3810
		400	550	6930
Example A82	Example A30	300	38400	35500
		320	3100	3110
		340	750	770
		360	360	390
		380	190	860
		400	230	2990

Comparative Examples A55-A57

[0234] Using the polyimide powders employed above in Comparative Examples A14-A16, their melt viscosities and the temperature dependency of their melt viscosity stability were ascertained in a similar manner as in Examples A80-A82.

[0235] The results are shown in Table A31.

Table A31

Comp.Ex. No.	Comp.Ex. No. of used powder	Measuring temp. [°C]	Melt viscosity [Pa · S]
			5min.	30min.
Comp.Ex. A55	Comp.Ex. A14	300	No flow	←
		320	62000	101000
		340	13900	No flow
		360	No flow	←
		380	No flow	←
		400	No flow	←
Comp.Ex. A56	Comp.Ex. A15	300	No flow	←
		320	16600	33100
		340	3450	No flow
		360	No flow	←
		380	No. flow	←
		400	No flow	←
Comp.Ex. A57	Comp.Ex. A16	300	37700	36400
		320	4020	10440
		340	1330	No flow
		360	7830	No flow
		380	No flow	←
		400	No flow	←

[0236] From the results of Examples A80-A82 and Comparative Examples A55-A57, it is evident that over a wide temperature range, the crosslinkable-group-containing polyimide according to the present invention has high stability in melt viscosity and hence, excellent moldability or formability.

Examples A83-A87

[0237] Using a melt viscoelasticity meter ("RDS-II" manufactured by Rheometrix Scientific F.E.) equipped with parallel plates (e.g., 25 mm disposable), the gel times of the powders polymerized in Examples A13-A17 were measured at various temperatures. Incidentally, the term "gel time" means a time which is required until a gel point is reached at a constant frequency and a given temperature. The term "gel point", in turn, means an intersecting point between lines G' and G" when storage modulus G' and loss modulus G" are 'each' plotted as a function of time t (min.).

[0238] The measurement was performed up to 2 hours at each temperature. The results are shown in Table A32. Incidentally, ">120" which appears in Table A32 indicates that no gel point was reached within the measuring time.

Table A32

Ex. No.	Ex. No. of used powder	Measuring temp. [°C]	Gel time [min.]
Example A83	Example A13	330	>120
		360	>120
		390	>120
Example A84	Example A14	330	>120
		360	>120
		390	52
Example A85	Example A15	330	>120
		360	112
		390	31
Example A86	Example A16	330	>120
		360	45
		390	17
Example A87	Example A17	330	>120
		360	22
		390	8

Comparative Examples A58-A59

[0239] The gel times of the powders, which were polymerized in Comparative Examples A6-A7, at various temperatures were measured in a similar manner as in Examples A83-A87. The results are shown in Table A33.

Table A33

Comp.Ex. No.	Comp.Ex. No. of used powder	Measuring temp. [°C]	Gel time [min.]
		330	55
Comp.Ex. A58	Comp.Ex. A6	360	6
		390	3
		330	15
Comp.Ex. A59	Comp.Ex. A7	360	3
		390	2

[0240] From the results of Examples A83-A87 and Comparative Examples A58-A59, it is evident that over a wide temperature range, the crosslinkable-group-containing polyimide according to the present invention is slow in gelation and hence, is excellent in moldability or formability.

Examples A88-A91, Comparative Examples A60-A63

[0241] Polyimide powder was obtained in exactly the same manner as in the reaction (A) described in Examples A46-A49 except that the amounts of the end blocking agents of the kinds were changed to only 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (69.50 g, 280.00 mmol). This polyimide powder will be identified by (C).

[0242] Further, the polyimide powder obtained in the reaction (B) described in Examples A46-A49 and the above-described polyimide (C) were blended at the ratios described in Table A34, respectively, whereby homogeneous mixed powders were obtained. These mixed powders will be identified by (D) and (E).

[0243] Physical properties of the mixed powders (C)-(E) are shown in Table A34.

Table A34

	Blending ratio (B)/(C) [wt/wt]	Logarithmic viscosity [dL/g]	Glass transition temp. [°C]	5% Weight loss temp. [°C]
(C)	---	0.427	234	560
(D)	50/50	0.426	234	560
(E)	10/90	0.426	234	560

[0244] The polyimide powders (D) and (E) obtained above were separately extruded into pellets in a similar manner as in Examples A46-A49, and their compression molding and chemical resistance test were performed.

[0245] The results are shown in Table A35.

Table A35

Ex./Comp.Ex. No.	Used powder	Compression molding conditions	Retention of break strength [%]
			Toluene	MEK
Example A88	(D)	390°C, 6 hr.	91.8	68.5
Example A89	(D)	370°C, 6 hr.	92.1	73.0
Example A90	(D)	350°C, 6 hr.	90.7	70.2
Example A91	(D)	330°C, 6 hr.	88.0	64.4
Comp.Ex. A60	(E)	390°C, 6hr.	78.3	42.2
Comp.Ex. A61	(E)	370°C, 6 hr.	82.0	42.6
Comp.Ex. A62	(E)	350°C, 6 hr.	81.4	43.3
Comp.Ex. A63	(E)	330°C, 6 hr.	80.3	45.9
[Note] In Table A35, "MEK" stands for methyl ethyl ketone.

[0246] From the above results, it is evident that crosslinkable-group-containing polyimides according to the present invention, which are available, from blending, can also be significantly improved in chemical resistance by annealing under various conditions irrespective of the annealing temperature. It is appreciated that this effect cannot be expected from the polyimides of the comparative examples.

Experiment B Series

[0247] In Example B1 to Example B62, a description will be made about certain examples out of the present invention, in each of which 50 to 100 mole % of recurring structural units in a backbone structure are of a recurring unit structure represented by:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group; and
   R represents a tetravalent aromatic group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, and at least one divalent linking group selected from the group of substituent groups represented by the following formulas:

Examples B1-B7, Comparative Examples B1-B3

[0248] In each of these examples and comparative examples, 3,4'-diaminodiphenyl ether (200.24 g, 1.000 mol), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (138.28g, 0.470 mol) and bis(3,4-dicarboxyphenyl) ether dianhydride (145.80 g, 0.470 mol) were charged as monomers together with the corresponding end blocking agent(s), the kind(s) and amount(s) of which are shown in Table B1, and m-cresol (1, 937 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and reactions were conducted under 200°C reflux conditions for 4 hours. In Table B1, "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)-acetylene anhydride.

Table B1

Ex./Comp.Ex. No.	Charged amount of PA		Charged amount of PCE		PA/PCE molar ratio
	[g]	[mmol]	[g]	[mmol]
Example B1	17.60	118.8	0.2979	1.200	99/1
Example B2	16.89	114.0	1,489	6.000	95/5
Example B3	16.00	108.0	2.979	12.00	90/10
Example B4	14.22	96.00	5.958	24.00	80/20
Example B5	10.66	72.00	11.92	48.00	60/40
Example B6	7.110	48.00	17.87	72.00	40/60
Example B7	3.555	24.00	23.83	96.00	20/80
Comp.Ex. B1	2.666	18.00	25.32	102.0	15/85
Comp.Ex. B2	0	0	29.79	120.0	0/100
Comp.Ex. B3	17.77	120.0	0	0	100/0

[0249] The temperature was then lowered to 190°C, at which the corresponding end blocking agent(s) shown in Table B1 was (were) charged again. The resulting contents were heated again, and the reactions were then conducted under 200°C reflux conditions for further 4 hours.

[0250] The reaction mixture was thereafter cooled to 100°C, the resulting viscous polymer solution was discharged into toluene (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in toluene (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 210°C for 12, hours under a nitrogen gas stream. The yield of the thus-obtained powder and the logarithmic viscosity number, glass transition temperature, 5% weight loss temperature and melt viscosity (360°C/5 min.) are shown in Table B2.

[0251] The present invention is characterized in that concerning the molecule ends, the molar ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is also evident that those having molar ratios of the chemical formula (2a) to the chemical formula (2b) greater than 80/20 are considerably inferior in moldability or formability to those having molar ratios of the chemical formula (2a) to the chemical formula (2b) equal to or smaller than 80/20.

Examples B8-B12, Comparative Examples B4,B5.

[0252] Using the powders obtained in Examples B2-B6 and Comparative Example B3, compression molding was conducted. The powders used in the respective examples and comparative examples are shown next in Table B3.

Table B3

Ex./Comp.Ex. No.	Ex./Comp.Ex. No. of used powder
Example B8	Example B2
Example B9	Example B3
Example B10	Example B4
Example B11	Example B5
Example B12	Example B6
Comp.Ex. B4,B5	Comp.Ex. B3

[0253] Described specifically, in each of these examples and comparative examples, the powder was extruded into pellets at 355°C by a single-screw extruder of 25 mm in barrel diameter. After the pellets were filled in a compression mold of configurations specified in ASTM-D-638, Compression molding was conducted at 360°C for 12 hours (Examples B8-B12, Comparative Example B4) or under conditions of 360°C and 5 minutes (Comparative Example 5). In all the examples and comparative examples, good molded products were obtained. Using those molded products, a tensile test was performed at room temperature (23°C). The results are shown in Table B4. In Table B4, "PA/PCE molar ratio" means the molar ratio of phthalic anhydride to 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride.

[0254] The present invention is characterized in that concerning the molecule ends, the molar ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is also evident that those having molar ratios of the chemical formula (2a) to the chemical formula (2b) not reaching 1/99 are inferior in mechanical properties to those having molar ratios of the chemical formula (2a) to the chemical formula (2b) equal to or greater than 1/99.

Examples B13-B17, Comparative Examples B6-B8

[0255] In each of these examples and comparative examples, 3,4'-diaminidiphenyl ether (200.24 g, 1.000 mol), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (138.28 g, 0.470 mol) and bis(3,4-dicarboxyphenyl) ether dianhydride (145.80 g, 0.470 mol) were charged as monomers together with m-cresol (1,737 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and a reaction was conducted under 200°C reflux conditions for 2 hours, whereby a solution of an end-unblocked polymer was obtained. During the reaction, the corresponding end blocking agent(s) described in Table B5 and m-cresol (200.0 mL) were charged into another vessel and were then heated beforehand at 100°C for 1 hour under a nitrogen atmosphere to provide a solution. The solution of the end blocking agent(s) was charged in its entirety into the solution of the end-unblocked polymer, and reaction(s) was(were) then conducted under 200°C reflux conditions for 2 hours. In Table B5, "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride.

Table B5

Ex./Comp.Ex. No.	Charged amount of PA		Charged amount of PCE		PA/PCE molar ratio
	[g]	[mmol]	[g]	[mmol]
Example B13	33.77	228.0	2.979	12.0	95/5
Example B14	31.99	216.0	5.958	24.0	90/10
Example B15	28.44	192.0	11.96	48.0	80/20
Example B16	21.33	144.0	23.83	96.0	60/40
Example B17	14.21	96.00	35.75	144.0	40/60
Comp.Ex. B6	5.332	36.00	50.64	204.0	15/85
Comp.Ex. B7	0	0	59.58	240.0	0/100
Comp.Ex. B8	35.55	240.0	0	0	100/0

[0256] The reaction mixture was thereafter cooled to 100°C. While maintaining the resultant viscous polymer solution at 100°C, toluene (2 liters) which had been heated at 100°C was charged into the polymer solution and further, toluene (6 liters) was charged dropwise over 4 hours. After toluene (4 liters) was charged, the resulting mixture was allowed to cool down to room temperature. A precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in toluene (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 200°C under reduced pressure for 12 hours under a gentle nitrogen gas stream. The yield of the thus-obtained powder and the logarithmic viscosity number, glass transition temperature, 5% weight loss temperature and melt viscosity (360°C/5 min.) are shown in Table B6.

[0257] The present invention is characterized in that concerning the molecule ends, the molar ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is also evident that those having molar ratios of the chemical formula (2a) to the chemical formula (2b) greater than 80/20 are considerably inferior in moldability or formability to those having molar ratios of the chemical formula (2a) to the chemical formula (2b) equal to or smaller than 80/20. Examples B18-B22, Comparative Examples B9/B10.

[0258] Using the powders obtained in Examples B13-B17 and Comparative Example B8, compression molding was conducted. The powders used in the respective examples and comparative examples are shown next in Table B7.

Table B7

Ex./Comp.Ex. No.	Ex./Comp.Ex. No. of used powder
Example B18	Example B13
Example B19	Example B14
Example B20	Example B15
Example B21	Example B16
Example B22	Example B17
Comp.Ex. B9,B10	Comp.Ex. B8

[0259] Described specifically, in each of these examples and comparative examples, the powder was extruded into pellets at 355°C by a single-screw extruder of 25 mm in barrel diameter. After the pellets were filled in a compression mold having a size of 10.0 mm in width and 80.0 mm in length, compression molding was conducted at 360°C for 12 hours (Examples B18-B22, Comparative Example B9) or under conditions of 360°C and 5 minutes (Comparative Example 10). In all the examples and comparative examples, good molded products were obtained. Those specimens were all of 10.0 mm ± 0.010 mm in width, 80.0 mm ± 0.010 mm in length and 1.500 mm ± 0.010 mm in thickness. Using those molded products, a chemical resistance test was performed. Described specifically, each specimen was held in place at portions 5.00 mm apart from opposite ends thereof, and was then adjusted and fixed such that a displacement of 3.50 mm in the direction of the thickness would be given when the specimen was bent by a jig maintained in contact with the specimen at a center thereof (a portion 40.0 mm apart from the respective, ends). Under those conditions, the specimen was immersed in toluene or methyl ethyl ketone. One hour, 24 hours and 168 hours later, the specimen was taken out of the solvent and visually observed for cracks.

[0260] The results of the chemical resistance test are shown in Table B8. In Table B8, "A", "B" and "C" indicate "completely free of cracks", "cracks observed in a very small number" and "cracks observed in a large number", respectively, in this order. Further, "PA/PCE molar ratio" means the molar ratio of phthalic anhydride to 1-phenyl-2-(3,4-dicarboxy-phenyl)acetylene anhydride, and "MEK" stands for methyl ethyl ketone.

Table B8

Ex./Comp.Ex. No.	Toluene immersion time			MEK immersion time			PA/PCE molar raitio
	1hr.	24hr.	168hr.	1hr.	24hr.	168hr.
Example B18	A	A	A	A	B	B	95/5
Example B19	A	A	A	A	A	B	90/10
Example B20	A	A	A	A	A	A	80/20
Example B21	A	A	A	A	A	A	60/40
Example B22	A	A	A	A	A	A	40/60
Comp.Ex.B9	A	A	B	B	C	C	0/100
Comp.Ex.B10	A	A	B	B	C	C	0/100

[0261] The present invention is characterized in that concerning the molecule ends, the molar ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is evident that those having molar ratios of the chemical formula (2a) to the chemical formula (2b) not reaching 1/99 are inferior in chemical resistance to those having molar ratios of the chemical formula (2a) to the chemical formula (2b) equal to or greater than 1/99.

Examples B23-B32, Comparative Examples B11-B16

[0262] In each of these examples and comparative examples, the following two reactions (A),(B) were conducted.

(A) 3,4-Diaminodiphenyl ether (200.24 g, 1.000 mol), 3,3',4, 4'-biphenyltetracarboxylic acid dianhydride (138.28 g, 0.470 mol) and 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (151.45 g, 0.470 mol) were charged as monomers together with phthalic anhydride (10.66 g, 72.00 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (11.92 g, 48.00 mmol) as end blocking agents, m-cresol (1,960 g) as a solvent, and γ-picoline (13.970 g, 0.1500 mol) as a catalyst into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 150°C over 2 hours under a nitrogen atmosphere, and reactions were conducted at 150°C for 2 hours.
As end blocking agents, phthalic anhydride (5.33 g, 36.00 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (5.96 g, 24.00 mmol) were then charged, followed by the reactions at 150°C for further 8 hours.
The reaction mixture was thereafter cooled to 60°C, the resulting viscous polymer solution was discharged into methyl ethyl ketone (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in methyl ethyl ketone (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 220°C for 12 hours under a nitrogen gas stream, whereby polyimide powder was obtained.

(B) In each of these examples and comparative examples, polyimide powder was obtained in exactly the same manner as in the reaction (A) except that upon preparation of the make-up, the amount(s) of the end blocking agent(s) of the kind(s) was(were) changed to only phthalic anhydride (17.77 g, 120.00 mmol) and that during the reactions, the amount(s) of the end blocking agent(s) of the kind(s) was(were) changed to only phthalic anhydride (8.89 g, 60.00 mmol).

[0263] The yields of the powders obtained in the two reactions (A), (B) and their logarithmic viscosity numbers, glass transition temperatures, 5% weight loss temperatures and melt viscosities (360°C/5 min.) are shown in Table B9.

[0264] Further, each powder was extruded into pellets at 355°C by a single-screw extruder of 25 mm in barrel diameter. After the pellets were filled in a compression mold of the shape specified in ASTM-D-638, compression molding was conducted under the conditions described in Table B10.

Table B10

Ex./Comp.Ex. No.	Used powder	Compression molding conditions
Examples B23,B28	(A)	350°C, 2 hr.
Examples B24,B29	(A)	350°C, 6 hr.
Examples B25,B30	(A)	350°C, 12 hr.
Examples B26,B31	(A)	350°C, 24 hr.
Examples B27,B32	(A)	350°C, 72 hr.
Comp.Ex. B11,B14	(B)	350°C, 2 hr.
Comp.Ex. B12,B15	(B),	350°C, 12 hr.
Comp.Ex. B13,B16	(B)	350°C, 72 hr.

[0265] Using the specimens so obtained, a tensile test at room temperature (23°C) and a high-temperature tensile test at 177°C were performed. The results are shown in Table B11.

[0266] From the foregoing, it is evident that the crosslinkable-group-containing polyimide according to the present invention can be significantly improved in roomtemperature and high-temperature mechanical properties by annealing, and it is also appreciated that this effect cannot be expected from the conventional polyimides of the comparative examples.

Examples B28-B32, Comparative Examples B14-B16

[0267] In each of these examples and comparative examples, bis(3,4-dicarboxyphenyl)ether dianhydride and 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride were charged in their corresponding amounts shown in Table B12 together with 4,4'-diaminodiphenyl ether (200.24 g, 1.000 mol), all as monomers, into a vessel equipped withe stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. As a solvent, m-cresol was also charged in its corresponding amount shown in Table B12. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and a reaction was conducted under 200°C reflux conditions for 2 hours, whereby a solution of an end-unblocked polymer was obtained. In Table B12, "ODPA" stands for bis(3,4-dicarboxyphenyl) ether dianhydride, and "HQDA" stands for 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride.

Table B12

Ex./Comp.Ex. No.	Charged amount of ODPA		Charged amount of HQDA		Charged amount of m-cresol [g]
	[g]	[mol]	[g]	[mol]
Example B28	208.47	0.6720	115.87	0.2880	1097
Examples B29,31	201.95	0.6510	112.25	0.2790	1057
Examples B30,32	195.44	0.6300	108.63	0.2700	1016
Comp.Ex.B14	208.47	0.6720	115.87	0.2880	1097
Comp.Ex.B15	201.95	0.6510	112.25	0.2790	1057
Comp.Ex.B16	195.44	0.6300	108.63	0.2700	1016

[0268] During the reaction, the corresponding end blocking agents described in Table B13 and m-cresol (200.0 mL) were charged into another vessel and were then heated beforehand at 100°C for 1 hour under a nitrogen atmosphere to provide a solution. The solution of the end blocking agents was charged in its entirety into the solution of the end-unblocked polymer, and reactions were then conducted under 200°C reflux conditions for 2 hours. In Table B13, "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)-acetylene anhydride.

Table B13

Ex./Comp.Ex. No.	Charged amount of PA		Charged amount of PCE		PA/PCE molar ratio
	[g]	[mmol]	[g]	[mmol]
Example B28	16.59	112.0	11.92	48.00	70/30
Example B29	29.03	196.0	20.85	84.00	70/30
Example B30	41.47	280.0	29.79	120.0	70/30
Example B31	20.74	140.0	34.75	140.0	50/50
Example B32	29.62.	200.0	49.45	200.0	50/50
Comp.Ex. B14	3.555	24.00	33.76	136.0	15/85
Comp.Ex. B15	6.221	42.00	59.08	238.0	15/85
Comp.Ex. B16	8.887	60.00	84.40	340.0	15/85

[0269] The reaction mixture was thereafter cooled to 60°C, the resulting viscous polymer solution was discharged into methyl thyl ketone (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in methyl ethyl ketone (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 220°C for 12 hours under a nitrogen gas stream, whereby polyimide powder was obtained.

[0270] The logarithmic viscosity number, glass transition temperature and melt viscosity (360°C/5 min., 15 min., 30 min.) of the thus-obtained polyimide powder are shown in Table B14.

[0271] It is appreciated from the results that the crosslinkable-group-containing polyimide according to the present invention, even at various molecular weights (or logarithmic viscosity numbers correlating with the molecular weights), has good melt fluidity and is better in moldability or formability than the polyimides of the comparative examples. Examples B33-B37, Comparative Examples B17-B19

[0272] In each of these examples and comparative examples, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride and N-methyl-2-pyrrolidone were charged in their corresponding amounts shown in Table B15 together with 3,4'-diaminodiphenyl ether (200.24 g, 1.000 mol) into a vessel equipped with a stirrer and a nitrogen gas inlet tube. While stirring the contents under a nitrogen atmosphere, a reaction was conducted at room temperature for 12 hours, whereby a polyamic acid varnish was obtained. The corresponding end blocking agents, the kind(s) and amount(s) of which are shown in Table B15, were charged into the thus-obtained varnish, followed by reactions at room temperature for 12 hours. In Table B15, "BPDA", "NMP", "PA" and "PCE" stand for pyromellitic dianhydride, N-methyl-2-pyrrolidone, phthalic anhydride, and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride, respectively.

[0273] The logarithmic viscosity number of the thus-obtained polyamic acid varnish is shown in Table B16.

[0274] Using that varnish, a film was prepared.

[0275] Described specifically, the varnish was evenly cast on a soft glass plate. Within an oven through which a nitrogen gas stream was flowing, the film was heated from 50°C to 200°C at a heating rate of 1°C per minute, and was then cured at 200°C for 2 hours. Further, the film was heated from 200°C to 410°C at a heating rate of 20°C per minute, and was then annealed at 410°C for 30 minutes. After the resulting film was quenched, hot water was poured over the film such that the film was peeled off from the glass plate. Incidentally, the film of Comparative Example 19 was so brittle that upon quenching, it shattered into small pieces, thereby failing to obtain a film. From the films of the remaining examples, good films were obtained.

[0276] A tensile test of each film, which had been obtained by the above-described procedures, was performed at room temperature (23°C). The results, are shown in Table B16.

[0277] From the above results, it is evident that the crosslinkable-group-containing polyimide according to the present invention, at various molecular weights (or logarithmic viscosity numbers correlating with the molecular weights), exhibits better physical properties than the polyimides of the comparative examples.

Examples B38-B42, Comparative Examples B20-B22

[0278] In each of these examples and comparative examples, 500 mL of the corresponding one of the varnishes - which had been obtained in Examples B33-B37 and Comparative Examples B17-B19, respectively - were discharged into methanol (10 liters) which was under vigorous agitation, and a precipitate was collected by filtration. The precipitate was washed further with methanol (800 mL). After provisional drying under reduced pressure at 50°C for 24 hours, the precipitate was dehydrated and imidated under reduced pressure at 250°C for 12 hours under a gentle nitrogen gas stream, whereby polyimide powder was obtained. The used varnish and the glass transition temperature and 5% weight loss temperature of the thus-obtained polyimide powder are shown in Table B17.

[0279] Further, the powder was placed on a heat-resistant dish, annealed under nitrogen gas at 420°C for 1 hour, and then quenched. Thereafter, its glass transition temperature and 5% weight loss temperature were measured. The results are shown in Table B17.

[0280] In Table B17, "Tg" indicates a glass transition temperature, and "Td5" designates a 5% weight loss temperature.

Table B17

Ex./Comp.Ex No.	Used varnish	Before annealing		After annealing
		Tg[°C],	Td5[°C]	Tg°C],	Td5[°C]
Example B38	Example B33	248	560	271	550
Example B39	Example B34	247	560	269	554
Example B40	Example B35	246	561	269	553
Example B41	Example B36	242	554	267	552
Example B42	Example B37	236	544	268	547
Comp.Ex.B20	Comp.Ex.B17	248	559	248	552
Comp.Ex.B21	Comp.Ex.B18	245	560	245	550
Comp.Ex.B22	Comp.Ex.B19	235	543	235	511

[0281] From these results, it is appreciated that, when annealed, the crosslinkable-group-containing polyimide according to the present invention is significantly improved in glass transition temperature but the polyimides of the comparative examples are not improved.

Examples B43-B45, Comparative Example B23

[0282] In each of these examples and comparative example, 3,4'-diaminodiphenyl ether (200.24 g, 1.000 mol) and 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (276.57 g, 0.940 mol) were charged as monomers together with m-cresol (1,707 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and a reaction was conducted under 200°C reflux conditions for 2 hours, whereby a solution of an end-unblocked polymer was obtained. During the reaction, the corresponding end blocking agent(s) described in Table B18 and m-cresol (200.0 mL) were charged into another vessel and were then heated beforehand at 100°C for 1 hour under a nitrogen atmosphere to provide a solution. The solution of the end blocking agent(s) was charged in its entirety into the solution of the end-unblocked polymer, and reaction(s) was(were) then conducted under 200°C reflux conditions for 2 hours. In Table B18; "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride.

Table B18

Ex./Comp.Ex. No.	Charged amount of PA		Charged amount of PCE		pA/pCE molar ratio
	[g]	[mmol]	[g]	[mmol]
Example B43	33.77	228.0	2.979	12.0	95/5
Example B44	31.99	216.0	5.958	24.0	90/10
Example B45	28.44	192.0	11.92	48.0	80/20
Comp.Ex. B23	17.77	120.0	0	0	100/0

[0283] The reaction mixture was thereafter cooled to 100°C. While maintaining the resultant viscous polymer solution at 100°C, toluene (4 liters) was charged dropwise into the polymer solution over 4 hours. After toluene (3 liters) which had been heated at 80°C was additionally charged, the resulting mixture was allowed to cool down to room temperature. Toluene (3 liters) was added further, followed by stirring for 1 hour. A precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in toluene (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 200°C under reduced pressure for 12 hours under a gentle nitrogen gas stream. The logarithmic viscosity number, glass transition temperature, crystal melting temperature, 5% weight loss temperature and melt viscosity (420°C/5 min.) of the thus-obtained polyimide powder are shown in Table B19.

[0284] Using the polyimide powder so obtained, pelletization was conducted at 420°C by extrusion. Injection molding was then conducted at a resin temperature of from 315 to 425°C, an injection pressure of from 1,400 to 1,600 kg/cm² and a mold temperature of 220, whereby a specimen of the shape specified in ASTM-D-638 was obtained.

[0285] To the thus-obtained specimen, annealing treatment was applied further under a nitrogen gas stream, whereby the specimen was crystallized and, where the specimen was that of one of the examples, the specimen was subjected to crosslinking. The annealing treatment consisted of the following seven steps: ① heating from room temperature to 240°C at a heating rate of 5°C/min., ② annealing at 240°C for 5 hours, ③ heating from 240°C to 300°C at a heating rate of 5°C/min., ④ annealing at 300°C for 5 hours, ⑤ heating from 300°C to 380°C at a heating rate of 5°C/min., ⑥ annealing at 380°C for 5 hours, and ⑦ cooling to room temperature at a cooling rate of 5°C/min.

[0286] Using the specimen, a tensile test was performed. The results are shown in Table B20.

[0287] From the above results, it is evident that the crosslinkable-group-containing polyimide according to the present invention, even when crystallized, has good mechanical properties.

Examples B46-B49, Comparative Examples B24-B27

[0288] In each of these examples and comparative examples, the following two reactions (A), (B) were conducted.

(A) 3,4'-diaminodiphenyl ether (200.24 g, 1.000 mol), 3,3',4,4'-biphenyltetracarboxylic acid anhydride (136.81 g, 0.465 mol) and bis(3,4-dicarboxyphenyl) ether dianhydride (144.25 g, 0.465 mol) were charged as monomers together with m-cresol (1,925 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 200°C over 3 hours under a nitrogen atmosphere, and a reaction was conducted under 200°C reflux conditions for 2 hours, whereby a solution of an end-unblocked polymer was obtained. During the reaction, phthalic anhydride (20.74 g, 140.0 mmol) and 1-phenyl-2- (3, 4-dicarboxyphenyl) acetylene anhydride (34.75 g, 140.0 mmol) were charged as end blocking agents together with m-cresol (200.0 mL) into another vessel, and were then heated beforehand at 100°C for 1 hour under a nitrogen atmosphere to provide a solution. The solution of the end blocking agents was charged in its entirety into the solution of the end-unblocked polymer, and reactions were then conducted under 200°C reflux conditions for 2 hours. The reaction mixture was thereafter cooled to 60°C, the resulting viscous polymer solution was discharged into methanol (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in methanol (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was. dried at 220°C for 12 hours under a nitrogen gas stream, whereby polyimide powder was obtained.

(B) In each of these examples and comparative examples, polyimide powder was obtained in exactly the same manner as in the reaction (A) except that the amounts of the end blocking agents of the kinds were changed to only phthalic anhydride (41.47 g, 280.00 mmol).

[0289] The logarithmic viscosity numbers, glass transition temperatures, 5% weight loss temperatures and melt viscosities (360°C/5 min.) of the powders obtained in the two reactions (A), (B) are shown in Table B21.

[0290] Further, each powder was extruded into pellets at 355°C by a 25-mm single-screw extruder. After the pellets were filled in a compression mold of the shape specified in ASTM-D-638, compression molding was conducted under the conditions described in Table B22. Using the thus-obtained specimen, a chemical resistance test was performed. Described specifically, the specimen was fixed on a jig in a state stretched by 0.5%, and was then immersed in toluene or methyl ethyl ketone at room temperature (23°C) for 24 hours. Using the immersed specimen, a tensile test was performed at room temperature (23°C). The results of the tensile test were compared with those of a tensile test of a corresponding non-immersed specimen, and a break strength retention (%) was calculated. Incidentally, the term "break strength retention (%)" as used herein means a value expressed in terms of percentage by comparing the break strength of an immersed specimen with the break strength of a corresponding non-immersed specimen.

[0291] The results are shown in Table B22. In Table B22, "MEK" stands for methyl ethyl ketone.

Table B22

Ex./Comp.Ex. No.	Used powder	Compression molding conditions	Retention of break strength [%]
			Toluene	MEK
Example B46	(A)	390°C, 6 hr.	90.6	77.4
Example B47	(A)	370°C, 6 hr.	90.2	81.0
Example B48	(A)	350°C, 6 hr.	87.6	75.1
Example B49	(A)	330°C, 6 hr.	84.1	66.5
Comp.Ex. B24	(B)	390°C, 6 hr.	80.8	37.1
Comp.Ex. B25	(B)	370°C, 6 hr.	83.2	41.2
Comp.Ex. B26	(B)	350°C, 6 hr.	82.6	42.4
Comp.Ex. B27	(B)	330°C, 6 hr.	83.0	40.7

[0292] From the above results, it is evident that the crosslinkable-group-containing polyimide according to the present invention is significantly improved in chemical resistance by annealing under various conditions irrespective of the annealing temperature. It is appreciated that this effect cannot be expected from the conventional polyimides of the comparative examples.

Examples B50-B54, Comparative Examples B28-B32

[0293] In each of these examples and comparative examples, polyimide powder was synthesized in exactly the same manner as in Examples B13-B17 except that the corresponding one of various diamines and bis(3,4-dicarboxyphenyl) ether dianhydride (288.50 g, 0.930 mol) were used as monomers and that phthalic anhydride (20.74 g, 140.0 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (34.75 g, 140.0 mmol) were used as end blocking agents in each of the examples but only phthalic anhydride (41.47 g, 280.00 mmol) was used as an end blocking agent in each of the comparative examples.

[0294] Further, the thus-obtained polyimide powder was extruded into pellets at 325°C to 365°C by a single-screw extruder of 25 mm in barrel diameter. After the pellets were filled in a compression mold of the shape specified in ASTM-D-648, compression molding was conducted under the conditions of 360°C and 6 hours.

[0295] Using the specimen so obtained, its heat distortion temperature was measured.

[0296] The kinds and amounts of the diamines, which were used in the respective examples and comparative examples, and the heat distortion temperatures are shown in Table B23. In Table B23, the diamines are represented by the following signs:

a) 3,3'-diaminodiphenyl ether,

b) 3,4'-diaminodiphenyl ether,

c) 4,4'-diaminodiphenyl ether,

e) 3,3'-diaminodiphenyl sulfone, and

h) 4,4'-diaminodiphenylmethane.

Examples B55-B59, Comparative Examples B33-B37

[0297] In each of these examples and comparative examples, polyimide powder was synthesized in exactly the same manner as in Examples 23-32 except that the corresponding one of various diamines, 4,4'-diaminodiphenyl ether (180.22 g, 0.900 mol) and 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (374.16 g, 0.930 mol) were used as monomers and that phthalic anhydride (20.74 g, 140.0 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)-acetylene anhydride (34.75 g, 140.0 mmol) were used as end blocking agents in each of the examples but only phthalic anhydride (41.47 g, 280.00 mmol) was used as an end blocking agent in each of the comparative examples.

[0298] In a similar manner as in Examples B50-B54, specimens were then obtained from the respective polyimide powders, and their heat distortion temperatures were measured. The kinds and amounts of the diamines, which were used in the respective examples, and the heat distortion temperatures are shown in Table B24. In Table B24, the diamines are indicated by the following signs:

a) 3,3'-diaminophenyl ether,

b) 4,4'-diaminodiphenyl ether,

c) 3,3'-diaminodiphenyl sulfide,

d) 3,3'-diaminobenzophenone,

e) 3,3'-diaminodiphenylmethane, and

f) 2,2-di(4-aminophenyl)propane.

[0299] From the above tests, it is evident that crosslinkable-group-containing polyimides according to the present invention, which have various structures, are considerably superior in heat resistance to similar polymers having no crosslinkable groups.

Examples B60-B61, Comparative Example B38

[0300] Using the polyimide powders employed above in Examples B30 and B32 and Comparative Example B16, their melt viscosities were measured in a similar manner as in Examples A80-A82.

[0301] Further, with respect to those powders, their gel times at various temperatures were measured in a similar manner as in Examples A83-A87.

[0302] The results are shown in Table B25. Incidentally, ">120" which appears in Table B25 indicates that no gel point was reached within the measuring time.

[0303] From the results, it is evident that over a wide temperature range, the crosslinkable-group-containing polyimide according to the present invention has high stability in melt viscosity and is resistant to gelation and hence, is excellent in moldability or formability.

Experiment C Series

[0304] In Example C1 to Example C39, a description will be made about certain examples out of the present invention, in each of which 50 to 100 mole % of recurring structural units in a backbone structure are of a recurring unit structure represented by:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond; a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group; and
   R represents a tetravalent aromatic group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group/consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, and at least one divalent linking group selected from the group of substituent groups represented by the following formulas:

Examples C1-C7, Comparative Examples C1-C3

[0305] In each of these examples and comparative examples, 1,3-bis(4-aminophenoxy)benzene (292.34 g, 1.000 mol), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (138.28 g, 0.470 mol) and bis(3,4-dicarboxyphenyl) ether dianhydride (145.80 g, 0.470 mol) were charged as monomers together with the corresponding end blocking agent(s), the kind(s) and amount(s) of which are shown in Table C1, and m-cresol (3,266 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and reactions were conducted under 200°C reflux conditions for 4 hours. In Table C1, "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)-acetylene anhydride.

Table C1

Ex./Comp.Ex. No.	Charged amount of PA		Charged of amount PCE		PA/PCE molar ratio
	[g]	[mmol]	[g]	[mmol]
Example C1	17.60	118.8	0.2979	1.200	99/1
Example C2	16.89	114.0	1.489	6.000	95/5
Example C3	16.00	108.0	2.979	12.00	90/10
Example C4	14.22	96.00	5.958	24.00	80/20
Example C5	10.66	72.00	11.92	48.00	60/40
Example C6	7.110	48.00	17.87	72.00	40/60
Example C7	3.555	24.00	23.83	96.00	20/80
Comp:Ex. C1	2.666	18.00	25.32	102.0	15/85
Comp.Ex. C2	0.0		29.79	120.0	0/100
Comp.Ex. C3	17.77	120.0	0.0		100/0

[0306] The temperature was then lowered to 190°C, at which the corresponding end blocking agent(s), the kind(s) and amount(s) of which are shown in Table C1, was(were) charged again. The resulting contents were heated again, and the reactions were then conducted under 200°C reflux conditions for further 4 hours. The reaction mixture was thereafter cooled to 100°C, the resulting viscous polymer solution was discharged into toluene (20 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in toluene (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 210°C for 12 hours under a nitrogen gas stream. The yield of the thus-obtained powder and the logarithmic viscosity number, glass transition temperature, 5% weight loss temperature and melt viscosity (360°C/5 min.) are shown in Table C2.

[0307] The present invention is characterized in that concerning the molecule ends, the molar ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is also evident that those having molar ratios of the chemical formula (2a) to the chemical formula (2b) greater than 80/20 are considerably inferior in moldability or formability to those having molar ratios of the chemical formula (2a) to the chemical formula (2b) equal to or smaller than 80/20. Examples C8-C12, Comparative Examples C4,C5.

[0308] Using the powders obtained in Examples C2-C6 and Comparative Example C3, compression molding was conducted. The powders used in the respective examples and comparative examples are shown next in Table C3.

Table C3

Ex./Comp.Ex. No.	Ex./Comp.Ex. No. of used powder
Example C8	Example C2
Example C9	Example C3
Example C10	Example C4
Example C11	Example C5
Example C12	Example C6
Comp.Ex. C4,C5	Comp.Ex. C3

[0309] Described specifically, in each of these examples and comparative examples, the powder was extruded into pellets at 355°C by a single-screw extruder of 25 mm in barrel diameter. After the pellets were filled in a compression mold of configurations specified in ASTM-D-638, compression molding was conducted at 360°C for 12 hours (Examples C8-C12, Comparative Example C4) or under conditions of 360°C and 5 minutes (Comparative Example C5). In all the examples and comparative examples, good molded products were obtained. Using those molded products, a tensile test was performed at room temperature (23°C). The results are shown in Table C4. In Table C4, "PA/PCE molar ratio" means the molar ratio of phthalic anhydride to 1-phenyl-2-(3,4-dicarboxyphenyl)-acetylene anhydride.

[0310] The present invention is characterized in that concerning the molecule ends, the molar ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/2 as recited in certain claims. From the above-described results, it is also evident that those having molar ratios of the chemical formula (2a) to the chemical formula (2b) not reaching 1/99 are inferior in mechanical properties to those having molar ratios of the chemical formula (2a) to the chemical formula (2b) equal to or greater than 1/99.

Examples C13-C17, Comparative Examples C6-C8

[0311] In each of these examples and comparative examples, 1,4-bis(4-aminophenoxy)benzene (292.34 g, 1.000 mol), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (138.28 g, 0.470 mol) and bis(3,4-dicarboxyphenyl) ether dianhydride (145.80 g, 0.470 mol) were charged as monomers together with m-cresol (2,105 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and a reaction was conducted under 200°C reflux conditions for 2 hours, whereby a solution of an end-unblocked polymer was obtained. During the reaction, the corresponding end blocking agent(s) described in Table C5 and m-cresol (200.0 mL) were charged into another vessel and were then heated beforehand at 100°C for 1 hour under a nitrogen atmosphere to provide a solution. The solution of the end blocking agent(s) was charged in its entirety into the solution of the end-unblocked polymer, and reaction (s) was (were) then conducted under 200°C reflux conditions for 2 hours. In Table C5, "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride.k

Table C5

Ex./Comp.Ex. No.	Charged amount of PA		Charged amount of PCE		PA/PCE molar ratio
	[g]	[mmol]	[g]	[mmol]
Example C13	33.77	228.0	2.979	12.0	95/5
Example C14	31.99	216.0	5.958	24.0	90/10
Example C15	28.44	192.0	11.96	48.0	80/20
Example C16	21.33	144.0	23.83	96.00	60/40
Example C17	14.21	96.00	35.75	144.0	40/60
Comp.Ex. C6	5.332	36.00	50.64	204.0	15/85
Comp.Ex. C7	0	0	59.58	240.0	0/100
Comp.Ex. C8	35.55	240.0	0	0	100/0

[0312] The reaction mixture was thereafter cooled to 100°C. While maintaining the resultant viscous polymer solution at 100°C, toluene (2 liters) which had been heated at 100°C was charged into the polymer solution and further, toluene (6 liters) was charged dropwise over 4 hours. After toluene (4 liters) was charged, the resulting mixture was allowed to cool down to room temperature. A precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in toluene (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 200°C under reduced pressure for 12 hours under a gentle nitrogen gas stream. The yield of the thus-obtained powder and the logarithmic viscosity number, glass transition temperature, 5% weight loss temperature and melt viscosity (360°C/5 min.) are shown in Table C6.

[0313] The present invention is characterized in that concerning the molecule ends, the molar ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is also evident that those having molar ratios of the chemical formula (2a) to the chemical formula (2b) greater than 80/20 are considerably inferior in moldability or formability to those having molar ratios of the chemical formula (2a) to the chemical formula (2b) equal to or smaller than 80/20. Examples C18-C22, Comparative Examples C9, C10.

[0314] Using the powders obtained in Examples C13-C17 and Comparative Example C8, compression molding was conducted. The powders used in the respective examples and comparative examples are shown next in Table C7.

Table C7

Ex./Comp.Ex. No.	Ex./Comp.Ex. No. of used powder
Example C18	Example C13
Example C19	Example C14
Example C20	Example C15
Example C21	Example C16
Example C22	Example C17
Comp.Ex. C9,C10	Comp.Ex. C8

[0315] Described specifically, in each of these examples and comparative examples, the powder was extruded into pellets at 355°C by a single-screw extruder of 25 mm in barrel diameter. After the pellets were filled in a compression mold having a size of 10.0 mm in width and 80.0 mm in length, compression molding was conducted at 360°C for 12 hours (Examples 18-22, Comparative Example 9) or under conditions of 360°C and 5 minutes (Comparative Example 10). In all the examples and comparative examples, good molded products were obtained. Those specimens were all of 10,0 mm ± 0.010 mm in width, 80.0 mm ± 0.010 mm in length and 1.500 mm ± 0.010 mm in thickness. Using those molded products, a chemical resistance test was performed. Described specifically, each specimen was held in place at portions 5.00 mm apart from opposite ends thereof, and was then adjusted and fixed such that a displacement of 3.50 mm in the direction of the thickness would be given when the specimen was bent by a jig maintained in contact with the specimen at a center thereof (a portion 40.0 mm apart from the respective ends). Under those conditions, the specimen was immersed in toluene or methyl ethyl ketone. One hour, 24 hours and 168 hours later, the specimen was taken out of the solvent and visually observed for cracks.

[0316] The results of the chemical resistance test are shown in Table C8. In Table C8, "A", "B" and "C" indicate "completely free of cracks", "cracks observed in a very small number" and "cracks observed in a large number", respectively, in this order. Further, "PA/PCE molar ratio" means the molar ratio of phthalic anhydride to 1-phenyl-2-(3,4-dicarboxy-phenyl)acetylene anhydride, and "MEK" stands for methyl ethyl ketone.

Table C8

Ex./Comp.Ex. No.	Toluene immersion time			MEK immersion time			PA/PCE molar ratio
	1hr.	24hr.	168hr.	1hr.	24hr.	168hr.
Example C18	A	A	A	B	B	B	95/5
Example C19	A	A	A	A	A	B	90/10
Example C20	A	A	A	A	A	B	80/20
Example C21	A	A	A	A	A	A	60/40
Example C22	A	A	A	A	A	A	40/60
Comp.Ex. C9	A	B	B	B	C	C	0/100
Comp.Ex. C10	A	B	B	B	C	C	0/100

[0317] The present invention is characterized in that concerning the molecule ends, the molar ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is evident that those having molar ratios of the chemical formula (2a) to the chemical formula (2b) not reaching 1/99 are inferior in chemical resistance to those having molar ratios of the chemical formula (2a) to the chemical formula (2b) equal to or greater than 1/99.

Examples C23-C27, Comparative Examples C11-C13

[0318] In each of these examples and comparative examples, the following two reactions (A), (B) were conducted.

(A) 1,3-Bis(3-aminophenoxy)benzene (292.34 g, 1.000 mol), pyromellitic dianhydride (102.52 g, 0.470 mol), and 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (151.45 g, 0.470 mol) were charged as monomers together with phthalic anhydride (10.66 g, 72.00 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (11.92 g, 48.00 mmol) as end blocking agents, m-cresol (2,185g) as a solvent, and γ-picoline (13.970 g, 0.1500 mol) as a catalyst into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 150°C, over 2 hours under a nitrogen atmosphere, and reactions were conducted at 150°C for 2 hours.
As end blocking agents, phthalic anhydride (5.33 g, 36.00 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (5.96 g, 24.00 mmol) were then charged, followed by the reactions at 150°C for further 8 hours.
The reaction mixture was thereafter cooled to 60°C, the resulting viscous polymer solution was discharged into methyl ethyl ketone (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in methyl ethyl ketone (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 220°C for 12 hours under a nitrogen gas stream, whereby polyimide powder was obtained.

(B) In each of these examples and comparative examples, polyimide powder was obtained in exactly the same manner as in the reaction (A) except that upon preparation of the make-up, the amount(s) of the end blocking agent(s) of the kind(s) was(were) changed to only phthalic anhydride (17.77 g, 120.00 mmol) and that during the reactions, the amount(s) of the end blocking agent (s) of the kind(s) was (were) changed to only phthalic anhydride (8.89 g, 60.00 mmol)

[0319] The yields of the powders obtained in the two reactions (A), (B) and their logarithmic viscosity numbers, glass transition temperatures, 5% weight loss temperatures and melt viscosities (360°C/5 min.) are shown in Table C9.

[0320] Further, each powder was extruded into pellets at 355°C by a single-screw extruder of 25 mm in barrel diameter. After the pellets were filled in a compression mold of the shape specified in ASTM-D-638, compression molding was conducted under the conditions described in Table C10.

Table C10

Ex./Comp.Ex. No.	Used powder	Compression molding conditions
Examples C23	(A)	345°C, 2 hr.
Examples C24	(A)	345°C, 6 hr.
Examples C25	(A)	345°C, 12 hr.
Examples C26	(A)	345°C, 24 hr.
Examples C27	(A)	345°C, 72 hr.
Comp.Ex. C11	(B)	345°C, 2 hr.
Comp.Ex. C12	(B)	345°C, 12 hr.
Comp.Ex. C13	(B)	345°C, 72 hr.

[0321] Using the specimens so obtained, a high-temperature, tensile test at room temperature (23°C) was performed. The results are shown in Table C11.

[0322] From the foregoing, it is evident that the crosslinkable-group-containing polyimide according to the present invention can be significantly improved in mechanical properties by annealing, and it is also appreciated that this effect cannot be expected from the conventional polyimides of the comparative examples.

Examples C28-C32, Comparative Examples C14-C16

[0323] In each of these examples and comparative examples, bis (3,4-dicarboxyphenyl) ether dianhydride and 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride were charged in their corresponding amounts shown in Table C12 together with 1,3-bis(4-aminophenoxy)benzene (292.34 g, 1.000 mol), all as monomers, into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. As a solvent, m-cresol was also charged in its corresponding amount shown in Table C12. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and a reaction was conducted under 200°C reflux conditions for 2 hours, whereby a solution of an end-unblocked polymer was obtained. In Table C12, "ODPA" stands for bis(3,4-dicarboxyphenyl) ether dianhydride, and "HQDA" stands for 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride.

Table C12

Ex./Comp.Ex. No.	Charged amount of ODPA		Charged amount of HQDA		Charged amount of m-cresol [g]
	[g]	[mol]	[g]	[mol]
Example C28	208.47	0.6720	115.87	0.2880	2267
Examples C29,31	201.95	0.6510	112.25	0.2790	2226
Examples C30,32	195.44	0.6300	108.63	0.2700	2186
Comp.Ex.C14	208.47	0.6720	115.87	0.2880	2267
Comp.Ex.C15	201.95	0.6510	112.25	0.2790	2226
Comp.Ex.C16	195.44	0.6300	108.63	0.2700	2186

[0324] During the reaction, the corresponding end blocking agents described in Table C13 and m-cresol (200.0 mL) were charged into another vessel and were then heated beforehand at 100°C for 1 hour under a nitrogen atmosphere to provide a solution. The solution of the end blocking agents was charged in its entirety into the solution of the end-unblocked polymer, and reactions were then conducted under 200°C reflux conditions for 2 hours. In Table C13, "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)-acetylene anhydride.

Table C13

Ex./Comp.Ex. No.	Charged amount of PA		Charged amount of PCE		PA/PCE molar ratio
	[g]	[mmol]	[g]	[mmol]
Example C28	16.59	112.0	11.92	48.00	70/30
Example C29	29.03	196.0.	20.85	84.00	70/30
Example C30	41.47	280.0	29.79	120.0	70/30
Example C31	20.74	140.0	34.75	140.0	50/50
Example C32	29.62	200.0	49.45	200.0	50/50
Comp.Ex. C14	3.555	24.00	33.76	136.0	15/85
Comp.Ex. C15	6.221	42.00	59.08	238.0	15/85
Comp.Ex. C16	8.887	60.00	84.40	340.0	15/85

[0325] The reaction mixture was thereafter cooled to 60°C, the resulting viscous polymer solution was discharged into methyl ethyl ketone (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in methyl ethyl ketone (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 220°C for 12 hours under a nitrogen gas stream, whereby polyimide powder was obtained.

[0326] The logarithmic viscosity number, glass transition temperature and melt viscosity (360°C/5 min., 15 min., 30 min.) of the thus-obtained polyimide powder are shown in Table C14.

[0327] It is appreciated from the results that the crosslinkable-group-containing polyimide according to the present invention, even at various molecular weights (or logarithmic viscosity numbers correlating with the molecular weights), has good melt fluidity and is better in moldability or formability than the polyimides of the comparative examples.

Examples C33-C37, Comparative Examples C17-C19

[0328] The powders which were obtained in Examples C28-C32 and Comparative Examples C14-C16 were separately placed on heat-resistant dishes, annealed under nitrogen gas at 420°C for 1 hour, and then quenched. Thereafter, their glass transition temperatures and 5% weight loss temperatures were measured. The results are shown in Table C15.

[0329] In Table C15, "Tg" indicates a glass transition temperature, and "Td5" designates a 5% weight loss temperature.

[0330] From these results, it is appreciated that, when annealed, the crosslinkable-group-containing polyimide according to the present invention is significantly improved in glass transition temperature but the polyimides of the comparative examples are not improved.

Examples C38-C39, Comparative Example C20

[0331] Using the polyimide powders employed above in Examples C29,C31 and Comparative Example C15, their melt viscosities were measured in a similar manner as in Examples A80-A82.

[0332] Further, with respect to those powders, their gel times at various temperatures were measured in a similar manner as in Examples A83-A87.

[0333] The results are shown in Table C16. Incidentally, ">120" which appears in Table C16 indicates that no gel point was reached within the measuring time.

[0334] From the results, it is evident that over a wide temperature range, the crosslinkable-group-containing polyimide according to the present invention has high stability in melt viscosity and is resistant to gelation and hence, is excellent in moldability or formability.

Experiment D Series

[0335] In Example D1 to Example D25, a description will be made about certain examples out of the present invention, in each of which 50 to 100 mole % of recurring structural units in a backbone structure are of a recurring unit structure represented by:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group.

Examples D1-D7, Comparative Examples D1-D3

[0336] In each of these examples and comparative examples, m-phenylenediamine (108.14 g, 1.000 mol) and 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride (378.18 g, 0.940 mol). were charged as monomers together with the corresponding end blocking agent(s), the kind(s) and amount(s) of which are shown in Table D1, and m-cresol (1,750 g) and N,N-dimethylacetamide (195 g) as solvents into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and reactions were conducted under 200°C reflux conditions for 4 hours. In Table D1, "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)-acetylene anhydride.

Table D1

Ex./Comp.Ex. No.	Charged amount of PA		Charged amount of PCE		PA/PCE molar ratio
	[g]	[mmol]	[g]	[mmol]
Example D1	17.60	118.8	0.2979	1.200	99/1
Example D2	16.89	114.0	1.489	6.000	95/5
Example D3	16.00	108.8	2.979	12.00	90/10
Example D4	14.22	96.00	5.958	24.00	80/20
Example D5	10.66	72.00	11.92	48.00	60/40
Example D6	7.110	48.00	17.87	72.00	40/60
Example D7	3.555	24.00	23.83	96.00	20/80
Comp.Ex. D1	2.666	18.00	25.32	102.0	15/85
Comp.Ex. D2	0	0	29.79	120.0	0/100
Comp.Ex. D3	17.77	120.0	0	0	100/0

[0337] The temperature was then lowered to 190°C, at which the corresponding end blocking agent (s), the kind(s) and amount(s) of which are shown in Table D1, was(were) charged again. The resulting contents were heated again, and the reactions were then conducted under 200°C reflux conditions for further 4 hours.

[0338] Thereafter, the reaction mixture was cooled to 100°C and then discharged into toluene (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in toluene (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 220°C for 12 hours under a nitrogen gas stream. The logarithmic viscosity number, glass transition temperature, 5% weight loss temperature and melt viscosity (360°C/5 min.) of the thus-obtained powder are shown in Table D2.

[0339] The present invention is characterized in that concerning the molecule ends, the molar ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is also evident that those having molar ratios of the chemical formula (2a) to the chemical formula (2b) greater than 80/20 are considerably inferior in moldability or formability to those having molar ratios of the chemical formula (2a) to the chemical formula (2b) equal to or smaller than 80/20.

Examples D8-D12, Comparative Examples D4,D5.

[0340] Using the powders obtained in Examples D2-D6 and Comparative Example D3, compression molding was conducted. The powders used in the respective examples and comparative examples are shown next in Table D3.

Table D3

Ex./Comp.Ex. No. Ex./Comp.Ex. No.	Ex./Comp.Ex.No. of used powder
Example D8	Example D2
Example D9	Example D3
Example D10	Example D4
Example D11	Example D5
Example D12	Example D6
Comp.Ex. D4,D5	Comp.Ex. D3

[0341] Described specifically, in each of these examples and comparative examples, the powder was extruded into pellets at 355°C by a 25-mm, single-screw extruder. After the pellets were filled in a compression mold of configurations specified in ASTM-D-638, compression molding was conducted at 360°C for 12 hours (Examples D8-D12, Comparative Example D4) or under conditions of 360°C and 5 minutes (Comparative Example 5). In all the examples and comparative examples, good molded products were obtained. Using those molded products, a tensile test was performed at room temperature (23°C). The results are shown in Table D4. In Table D4, "PA/PCE molar ratio" means the molar ratio of phthalic anhydride to 1-phenyl-2-(3,4-dicarboxyphenyl)-acetylene anhydride.

[0342] The present invention is characterized in that concerning the molecule ends, the molar ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is also evident that those having molar ratios of the chemical formula (2a) to the chemical formula (2b) not reaching 1/99 are inferior in mechanical properties to those having molar ratios of the chemical formula (2a) to the chemical formula (2b) equal to or greater than 1/99.

Examples D13-D22, Comparative Examples D6-D10

[0343] In each of these examples and comparative examples, the following two reactions (A), (B) were conducted.

(A) m-Phenylenediamine (108.14 g, 1.000 mol), 3,4'-diaminodiphenyl ether (80.10 g, 0.400 mol) and bis(3,4-dicarboxyphenyl) sulfone dianhydride (336.78 g, 0.940 mol) were charged as monomers together with phthalic anhydride (10.66 g, 72.00 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (11.92 g, 48.00 mmol) as end blocking agents, m-cresol (2,730 g) as a solvent, and γ-picoline (13.970 g, 0.1500 mol) as a catalyst into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 150°C over 2 hours under a nitrogen atmosphere, and reactions were conducted at 150°C for 2 hours.
As end blocking agents, phthalic anhydride (5.33 g, 36.00 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (5.96 g, 24.00 mmol) were then charged, followed by the reactions at 150°C for further 8 hours. The reaction mixture was thereafter cooled to 60°C and then discharged into methyl ethyl ketone (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in methyl ethyl ketone (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 220°C for 12 hours under a nitrogen gas stream, whereby polyimide powder was obtained.

(B) In each of these examples and comparative examples, polyimide powder was obtained in exactly the same manner as in the reaction (A) except that upon preparation of the make-up, the amount(s) of the end blocking agent(s) of the kind(s) was(were) changed to only phthalic anhydride (17.77 g, 120.00 mmol) and that during the reactions, the amount(s) of the end blocking agent(s) of the kind(s) was(were) changed to only phthalic anhydride (8.89 g, 60.00 mmol).

[0344] The yields of the powders obtained in the two reactions (A), (B) and the logarithmic viscosity numbers, glass transition temperatures, 5% weight loss temperatures and melt viscosities (360°C/5 min.) of the polyimide powders are shown in Table D5.

[0345] Further, each powder was extruded into pellets at 355°C by a 25-mm, single-screw extruder. After the pellets were filled in a compression mold of the shape specified in ASTM-D-638, compression molding was conducted under the conditions described in Table D6.

Table D6

Ex./Comp.Ex. No.	Used powder	Compression molding conditions
Examples D13, D18	(A)	360°C, 72 hr.
Examples D14, D19	(A)	360°C, 24 hr.
Examples D15, D20	(A)	360°C, 12 hr.
Examples D16, D21	(A)	360°C, 6 hr.
Examples D17, D22	(A)	360°C, 2 hr.
Comp.Ex. D6, D9	(B)	360°C, 72 hr.
Comp.Ex. D7, D10	(B)	360°C, 12 hr.
Comp.Ex. D8, D11	(B)	360°C; 2 hr.

[0346] Using the specimens so obtained, a tensile test at room temperature (23°C) and a high-temperature tensile test at 177°C were performed. The results are shown in Table D7.

[0347] From the above results, it is evident that, when annealed, the crosslinkable-group-containing polyimide according to the present invention is significantly improved in room-temperature and high-temperature mechanical properties. It is also appreciated that this effect cannot be expected from the conventional polyimides of the comparative examples.

Examples D23-25, Comparative Examples D12-13

[0348] Using the polyimide powders employed above in Examples D4-D6 and Comparative Example D1,D3, their melt viscosities were measured in a similar manner as in Examples A80-A82.

[0349] Further, with respect to those powders, their gel times at various temperatures were measured in a similar manner as in Examples A83-A87.

[0350] Further, those powders were separately extruded into pellets under conditions of 320°C to 360°C, and compression molding and an MEK resistance test were performed in a similar manner as in Examples A18-A22.

[0351] The results are shown in Table D8. Incidentally, ">120" which appearsin Table D8 indicates that no gel point was reached within the measuring time.

[0352] From the results, it is evident that over a wide temperature range, the crosslinkable-group-containing polyimide according to the present invention has is also excellent in chemical resistance despite their high stability in melt viscosity, good resistance to gelation and excellent moldability or formability over a wide temperature range.

Experiment E Series

[0353] In Example E1 to Example E22, a description will be made about certain examples out of the present invention, in each of which 50 to 100 mole % of recurring structural units in a backbone structure are of a recurring unit structure represented by:

wherein X, Z and R are groups to be indicated next, respectively, that is,
   X represents a divalent linking group selected from the group consisting of an ether group and an isopropylidene group;
   Z represents a divalent linking group selected from the group consisting of:

and
   R represents a tetravalent aromatic group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group,.a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group, and a position of each bond, said position being unspecified, is a para-position or meta-position.

Examples E1-E7, Comparative Examples E1-E3

[0354] In each of these examples and comparative examples, 1,3-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene (528.69 g, 1.000 mol) and 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (276.57 g, 0.940 mol) were charged as monomers together with the corresponding end blocking agent(s), the kind(s) and amount(s) of which are shown in Table E1, and m-cresol (3,220 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas. inlet tube. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and reactions were conducted under 200°C reflux conditions for 4 hours. In Table E1, "PA" stands for phthalic anhydride, and "PCE" stands for 1-phenyl-2-(3,4-dicarboxyphenyl)-acetylene anhydride.

Table E1

Ex./Comp.Ex. No.	Charged amount of PA		Charged amount of PCE		PA/pCE molar ratio
	[g]	[mmol]	[g]	[mmol]
Example E1	17.60	118.8	0.2979	1.200	99/1
Example E2	16.89	114.0	1.489	6.000	95/5
Example E3	16.00	108.0	2.979	12.00	90/10
Example E4	14.22	96.00	5.958	24.00	80/20
Example E5	10.66	72.00	11.92	48.00	60/40
Example E6	7.110	48.00	17.87	72.00	40/60
Example E7	3.555	24.00	23.83	96.00	20/80
Comp.Ex. E1	2.666	18.00	25.32	102.0	15/85
Comp.Ex. E2	0	0	29.79	120.0	0/100
Comp.Ex. E3	17.77	120.0	0	0	100/0

[0355] The temperature was then lowered to 190°C, at which the corresponding end blocking agent (s), the kind (s) and amount (s) of which are shown in Table E1, was (were) charged again. The resulting contents were heated again, and the reactions were then conducted under 200°C reflux conditions for further 4 hours.

[0356] Thereafter, the reaction mixture was cooled to 100°C and then discharged into toluene (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in toluene (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 220°C for 12 hours under a nitrogen gas stream. The logarithmic viscosity number, glass transition temperature, 5% weight loss temperature and melt viscosity (360°C/5 min.) of the thus-obtained powder are shown in Table E2.

[0357] The present invention is characterized in that concerning the molecule ends, the molar ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is also evident that those having molar ratios of the chemical formula (2a) to the chemical formula (2b) greater than 80/20 are considerably inferior in moldability or formability to those having molar ratios of the chemical formula (2a) to the chemical formula (2b) equal to or smaller than 80/20. Examples E8-E12, Comparative Examples E4,E5.

[0358] Using the powders obtained in Examples E2-E6 and Comparative Example E3, compression molding was conducted. The powders used in the respective examples and comparative examples are shown next in Table E3.

Table E3

Ex./Comp.Ex. No.	Ex./Comp.Ex. No. of used powder
Example E8	Example E2
Example E9	Example E3
Example E10	Example E4
Example E11	Example E5
Example E12	Example E6
Comp.Ex. E4,E5	Comp.Ex. E3

[0359] Described specifically, in each of these examples and comparative examples, the powder was extruded into pellets at 355°C by a 25-mm, single-screw extruder. After the pellets were filled in a compression mold of configurations specified in ASTM-D-638, compression molding was conducted at 360°C for 12 hours (Examples E8-E12, Comparative Example E4) or under conditions of 360°C and 5 minutes (Comparative Example E5). In all the examples and comparative examples, good molded products were obtained. Using those molded products, a tensile test was performed at room temperature (23°C). The results are shown in Table E4. In Table E4, "PA/PCE molar ratio" means the molar ratio of phthalic anhydride to 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride.

[0360] The present invention is characterized in that concerning the molecule ends, the molar ratio of the chemical formula (2a) to the chemical formula (2b) ranges from 1/99 to 80/20 as recited in certain claims. From the above-described results, it is also evident that those having molar ratios of the chemical formula (2a) to the chemical formula (2b) not reaching 1/99 are inferior in mechanical properties to those having molar ratios of the chemical formula (2a) to the chemical formula (2b) equal to or greater than 1/99. Examples E13-E22, Comparative Examples E6-E11

[0361] In each of these examples and comparative examples, the following two reactions (A),(B) were conducted.

(A) 4,4'-Bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]-diphenyl sulfone (668.85 g, 1,000 mol) and pyromellitic dianhydride (205.03 g, 0.940 mol) were charged as monomers together with phthalic anhydride (10.66 g, 72.00 mmol) and 1-phenyl-2-(3,4-dicarboxy-phenyl)acetylene anhydride (11.92 g, 48.00 mmol) as end blocking agents, m-cresol (2, 730 g) as a solvent, and γ-picoline (13.970 g, 0.1500 mol) as a catalyst into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 150°C over 2 hours under a nitrogen atmosphere, and reactions were conducted at 150°C for 2 hours.
As end blocking agents, phthalic anhydride (5.33 g, 36.00 mmol) and 1-phenyl-2-(3,4-dicarboxyphenyl)acetylene anhydride (5.96 g, 24.40 mmol) were then charged, followed by the reactions at 150°C for further 8 hours.
The reaction mixture was thereafter cooled to 60°C and then discharged into methyl ethyl ketone (10 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in methyl ethyl ketone (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 220°C for 12 hours under a nitrogen gas stream, whereby polyimide powder was obtained.

(B) In each of these examples and comparative examples, polyimide powder was obtained in exactly the same manner as in the reaction (A) except that upon preparation of the make-up, the amount(s) of the end blocking agent(s) of the kind(s) was(were) changed to only phthalic anhydride (17.77 8,120.00 mmol) and that during the reactions, the amount(s) of the end blocking agent(s) of the kind(s) was(were) changed to only phthalic anhydride (8.89 g, 60.00 mmol).

[0362] The yields of the powders obtained in the two reactions (A), (B) and the logarithmic viscosity numbers, glass transition temperatures, 5% weight loss temperatures and melt viscosities (360°C/5 min.) of the polyimide powders are shown in Table E5.

[0363] Further, each powder was extruded into pellets at 355°C by a 25-mm, single-screw extruder. After the pellets were filled in a compression mold of the shape specified in ASTM-D-638, compression molding was conducted under the conditions described in Table E6.

Table E6

Ex./Comp.Ex: No.	Used powder	Compression molding conditions
Examples E13, E18	(A)	360°C, 72 hr.
Examples E14, E19	(A)	360°C, 24 hr.
Examples E15, E20	(A)	360°C, 12 hr.
Examples E16, E21	(A)	360°C, 6 hr.
Examples E17, E22	(A)	360°C, 2 hr.
Comp.Ex. E6, E9	(B)	360°C, 72 hr.
Comp.Ex. E7, E10	(B)	360°C, 12 hr.
Comp.Ex. E8, E11	(B)	350°C, 2 hr.

[0364] Using the specimens so obtained, a tensile test at room temperature (23°C) and a high-temperature tensile test at 177°C were performed. The results are shown in Table E7.

[0365] From the above results, it is evident that, when annealed, the crosslinkable-group-containing polyimide according to the present invention is significantly improved in room-temperature and high-temperature mechanical properties. It is also appreciated that this effect cannot be expected from the conventional polyimides of the comparative examples.

Experiment F Series

[0366] In Example F1 to Example F16, a description will be made about certain examples out of the present invention, in each of which as crosslinkable-group-containing end blocking agent(s), one or more end blocking agents other than those represented by the chemical formula (2a) are used or one or more end blocking agents other than those represented by the chemical formula (2a) are used in combination.

[0367] In each of these examples arid comparative example, a 15% (W/W) polyamic acid varnish was obtained in a similar manner as in Examples A33-A37 by using dimethylacetamide as a solvent and 4,4'-bis(3-aminophenoxy)biphenyl (368.43 g, 1.000 mol), pyromellitic dianhydride (142.00 g, 0.651 mol) and 3,3',4,4'-benzophenonetetracarboxylic acid dianhydride (89.90 g, 0.279 mol) as monomers together with the corresponding end blocking agent(s) the amount(s) and kind(s) of which are shown in Table A29.

[0368] Using the thus-obtained varnishes, films were prepared under similar conditions as in Examples 33-37. Employing those films, a chemical resistance test was performed in toluene in a similar manner as in Examples A70-A75. The results are shown together with the logarithmic viscosity numbers of the varnishes in Table F1.

[0369] Incidentally, "A", "B" and "C" in Table F1 indicate "completely free of cracks", "cracks observed in a very small number" and "cracks observed in a large number", respectively, in this order.

[0370] From the above results, it is evident that crosslinkable-group-containing polyimides according to the present invention, which have various structures, are far superior in chemical resistance to similar polymers having no crosslinkable groups.

Examples F7-F10, Comparative Example F2

[0371] In each of these examples and comparative example, 1,3-bis(4-aminophenoxy)benzene (292.34 g, 1.000 mol), 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (158.87 g, 0.540 mol), bis(3,4-dicarboxyphenyl) ether dianhydride (167.51 g, 0.540 mol) were charged as monomers together with N-methyl-2-pyrrolidone (3,506 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen inlet tube. The contents were stirred for 12 hours under a nitrogen atmosphere. The end blocking agent(s), the kind(s) and amount(s) of which are shown in Table F2, was (were) charged, followed by stirring for 12 hours under a nitrogen atmosphere.

[0372] To the polymer solution so obtained, acetic anhydride (408 g) and γ-picoline (23.5g) were added, followed by stirring at 60°C for 3 hours under a nitrogen atmosphere.

[0373] The resultant viscous polymer solution was discharged into toluene (20 liters) which was under vigorous agitation, and a precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in toluene (4 liters). After the reprecipitate was collected by filtration and then provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 150°C under reduced pressure for 12 hours under a gentle nitrogen gas stream.

[0374] Using the polyimide powders so obtained, their gel times at 150°C were measured in exactly the same manner as in Examples A83-A87.

[0375] The results are shown together with the logarithmic viscosity numbers of the thus-obtained polyimide powders in Table F2. Incidentally, ">120" which appears in Table F2 indicates that no gel point was reached within the measuring time.

[0376] From the results, it is evident that the crosslinkable-group-containing polyimide according to the present invention is resistant to gelation and hence, is excellent in moldability or formability.

Examples F11-F16, Comparative Example F3

[0377] In each of these examples and comparative examples, 4,4'-bis(3-aminophenoxy)biphenyl (368.43 g, 1.000 mol), pyromellitic dianhydride (102.52 g, 0.470 mol) and 3,3',4,4'-biphenyltetracarboxylic acid dianhydride (138.28 g, 0.470 mol) were charged as monomers together with m-cresol (1,630 g) as a solvent into a vessel equipped with a stirrer, a reflux condenser, a water trap and a nitrogen gas inlet tube. The contents were heated with stirring to 200°C over 2 hours and 30 minutes under a nitrogen atmosphere, and a reaction was conducted under 200°C reflux conditions for 2 hours, whereby a solution of an end-unblocked polymer was obtained. During the reaction, the corresponding end blocking agent(s) described in Table F3 and m-cresol (200.0 mL) were charged into another vessel and were then heated beforehand at 100°C for 1 hour under a nitrogen atmosphere to provide a solution. The solution of the end blocking agent(s) was charged in its entirety into the solution of the end-unblocked polymer, and reaction(s) was(were) then conducted under 200°C reflux conditions for 2 hours.

[0378] The reaction mixture was thereafter cooled to 100°C. While maintaining the resultant viscous polymer solution at 100°C, toluene (4 liters) was charged dropwise into the polymer solution over 4 hours. After toluene (3 liters) which had been heated at 80°C was charged, the resulting mixture was allowed to cool down to room temperature. Toluene (3 liters) was added further, followed by stirring for 1 hour. A precipitate was then collected by filtration. The precipitate was again suspended and allowed to reprecipitate in toluene (4 liters). After the reprecipitate was collected by filtration and then' provisionally dried at 50°C for 24 hours, the reprecipitate was dried at 200°C under reduced pressure for 12 hours under a gentle nitrogen gas stream.

[0379] Using the polyimide powders so obtained, their gel times at 360°C were measured in exactly the same manner as in Examples A83-A87.

[0380] The results are shown together with the logarithmic viscosity numbers of the thus-obtained polyimide powders in Table F3.

[0381] From the foregoing, it is evident that the crosslinkable-group-containing polyimide according to the present invention is excellent in moldability or formability although its gel time is observed to vary somewhat depending on the crosslinkable groups. It is also appreciated that the polyimide of the comparative example undergoes quick gelation and its melt moldability or formability is hence extremely poor.

[0382] The present invention has made it possible to provide crosslinked thermoplastic polyimides having various excellent properties inherent to polyimides, namely, high heat resistance, excellent mechanical properties, superb sliding property, low water absorption property, outstanding electrical properties, high thermal oxidation resistance, high chemical resistance and high radiation resistance, especially those improved more markedly in heat resistance, chemical resistance and mechanical properties, melt-moldable or formable, crosslinkable-group-containing polyimides, crosslinkable-group-containing polyamic acids as precursors of the crosslinkable-group-containing polyimides, and production processes thereof.

Claims

1. A crosslinkable-group-containing polyimide comprising crosslinkable groups at 1 to 80 mole % of molecule ends thereof.

2. A crosslinkable-group-containing polyimide according to claim 1, wherein a backbone structure which forms said polyimide is substantially provided with thermoplasticity.

3. A crosslinkable-group-containing polyimide according to claim 1 or 2, said polyimide permitting melt molding or forming, wherein 1 to 80 mole % of said molecule ends are crosslinkable-group-containing molecule ends represented by the chemical formula (2a) and 99 to 20 mole % of said molecule ends are crosslinking-group-free molecule ends represented by the chemical formula (2b):

   wherein Y represents a trivalent aromatic group selected from the group consisting:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group; and

wherein T represents a divalent aromatic group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

4. A crosslinkable-group-containing polyimide according to anyone of claims 1-3, wherein said polyimide comprises polyimide molecules of a structure represented by the chemical formula (2c) :

wherein T, PI and Y are groups to be indicated next, respectively, that is,
   T represents a divalent aromatic group selected from the group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group;
   PI represents a polyimide backbone; and
   Y represents a trivalent aromatic group selected from the group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

5. A crosslinkable-group-containing polyimide according to claim 3 or 4, wherein in the chemical formula (2b) or (2c), T is the following chemical formula (2d):

6. A crosslinkable-group-containing polyimide according to any one of claims 3-5, wherein in the chemical formula (2a) or (2c), Y is the following chemical formula (2e):

7. A crosslinkable-group-containing polyimide according to any one of claims 1-6, wherein a backbone of said polyimide has recurring structural units represented by the chemical formula (1):

wherein Ar and R are groups to be described next, that is,
   Ar represents a divalent aromatic group selected from the group consisting of:

   wherein J represents a divalent linking group selected from the group consisting of a carbonyl group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group, K represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group, p and q each independently stand for 0 or 1, and a position of each bond, said position being unspecified, is a para-position or meta-position; and
   R represents a tetravalent aromatic group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group.

8. A crosslinkable-group-containing polyimide according to claim 7, wherein 50 to 100 mole % of said recurring structural units represented by the chemical formula (1) are of a recurring unit structure represented by the chemical formula (1a):

wherein G is a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group.

9. A crosslinkable-group-containing polyimide according to claim 8, wherein in the chemical formula (1a), G is a 4'-oxy-4-biphenoxy group.

10. A crosslinkable-group-containing polyimide according to claim 8, wherein in the chemical formula (1a), G is a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group.

11. A crosslinkable-group-containing polyimide according to claim 7, wherein 50 to 100 mole % of said recurring structural units represented by the chemical formula (1) are of a recurring unit structure represented by the chemical formula (1b):

wherein X and R are groups to be indicated next, respectively, that is,
   X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group; and
   R represents a tetravalent linking group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group,
   and a position of each bond, said position being unspecified, is a para-position or meta-position.

12. A crosslinkable-group-containing polyimide according to claim 11, wherein in the chemical formula (1b),
   X is an oxygen atom;
   imido-bonded positions of two benzenes to which X is directly bonded are a m-position and a p-position, respectively; and
   R is a 3,4,3',4'-substituted biphenyl.

13. A crosslinkable-group-containing polyimide according to claim 7, wherein among said recurring structural units represented by the chemical formula (1), 50 to 100 mole % are of a recurring unit structure represented by the chemical formula (1c):

wherein X and R are groups to be indicated next, respectively, that is,
   X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group; and
   R represents a tetravalent linking group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group, and a position of each bond, said position being unspecified, is a para-position or meta-position.

14. A crosslinkable-group-containing polyimide according to claim 13, wherein in the chemical formula (1c), X is an oxygen atom.

15. A crosslinkable-group-containing polyimide according to claim 13, wherein in the chemical formula (1c),
   X is an oxygen atom;
   positions of a benzene ring, at which two Xs are directly bonded, respectively, are m-positions relative to each other;
   bonded positions of each of two benzenes to each of which X and an imido group are directly bonded are p-positions relative to each other; and
   R is a 3,4,3',4'-substituted biphenyl.

16. A crosslinkable-group-containing polyimide according to claim 7, wherein among said recurring structural units represented by the chemical formula (1), 50 to 100 mole % are of a recurring unit structure represented by the chemical formula (1e):

wherein Q, Z and R are groups to be indicated next, respectively, that is,
   Q represents a divalent aromatic group selected from the group consisting of an ether group and an isopropylidene group;
   Z represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group; a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, and

   R represents a tetravalent aromatic group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a 4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group,
   and a position of each bond, said, position being unspecified, is a para-position or meta-position.

17. A crosslinkable-group-containing polyimide according to claim 16, wherein in the chemical formula (1e),
   Q is an oxygen atom; and
   Z is at least one divalent group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

18. A crosslinkable-group-containing polyimide according to claim 16, wherein in the chemical formula (1e),

Q   is an oxygen atom;

Z   is a direct bond; and

R   is a 1,2,4,5-substituted benzene.

19. A process for the production of a melt-moldable or formable, crosslinkable-group-containing polyimide, 1 to 80 mole % of molecule ends of said polyimide being crosslinkable-group-containing molecule ends represented by a chemical formula (2a). and 99 to 20 mole % of said molecule ends being crosslinkable-group-free molecule ends represented by a chemical formula (2b), which comprises end-blocking ends of polyimide backbones by using dicarboxylic acid anhydrides represented by the chemical formula (3a) and the chemical formula (3b):

wherein Y represents a trivalent aromatic group selected from the group consisting:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group;

wherein T represents a divalent aromatic group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group;

wherein Y represents a trivalent aromatic group selected from the group consisting:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group; and

wherein T represents a divalent aromatic group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

20. A process according to claim 19, wherein said dicarboxylic acid anhydrides represented by the chemical formula (3a) and the chemical formula (3b) are used in amounts represented, on a molar ratio basis, by the numerical formula [1]:
   1/99 ≦ the dicarboxylic acid anhydride represented by the chemical formula (3a)/the dicarboxylic acid anhydride represented by the chemical formula (3b) ≦ 80/20 [1]

   Y represents a trivalent aromatic group selected from the group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

   T represents a divalent aromatic group selected from the group consisting of:

   wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, and a hexafluoroisopropylidene group.

21. A process according to claim 19 or 20, wherein in the chemical formula (3a) and/or the chemical formula (3b), T is the chemical formula (2a) and/or Y is the chemical formula (2e) :

22. A process according to any one of claims 19-21, wherein said polyimide backbones have been obtained by thermally and/or chemically imidating a polyamic acid obtained as a polyimide precursor by polymerizing a diamine component and a tetracarboxylic acid anhydride component.

23. A process according to claim 22, wherein said diamine component is at least one diamine component selected from the group consisting of diamine components represented by the chemical formula (4):

        H₂N-Ar-NH₂     (4)

wherein Ar represents a divalent aromatic group selected from the group consisting of:

   wherein J represents a divalent linking group selected from the group consisting of a carbonyl group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group, K represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group, p and q each independently stand for 0 or 1,
   and a position of each bond, said position being unspecified, is a para-position or meta-position.

24. A process according to claim 23, wherein of said diamine component represented by the chemical formula (4), 50 to 100 mole % are represented by the chemical formula (4c):

wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group, and
a position of each bond, said position being unspecified, is a para-position or meta-position.

25. A process according to claim 24, wherein in the chemical formula (4c), X is an oxygen atom.

26. A process according to claim 24, wherein in the chemical formula (4c),
   X is an oxygen;
   positions of a benzene ring, at which two Xs are directly bonded, respectively, are m-positions relative to each other; and
   bonded positions of each of two benzenes to each of which X and an amino group are directly bonded are p-positions relative to each other.

27. A process according to claim 24, wherein of the diamine component represented by the chemical formula (4), 50 to 100 mole % are represented by the chemical formula (4d):

wherein X represents a divalent linking group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group and a hexafluoroisopropylidene group.

28. A process according to claim 27, wherein in the chemical formula (4d), X is a direct bond.

29. A process according to claim 22, wherein said tetracarboxylic acid dihydride component is represented by the chemical formula (5):

wherein R represents a tetravalent linking group selected from the group consisting of:

   wherein G represents a divalent aromatic group selected from the group consisting of a direct bond, a carbonyl group, a sulfone group, a sulfide group, an ether group, an isopropylidene group, a hexafluoroisopropylidene group, a 3-oxyphenoxy group, a 4-oxyphenoxy group, a 4'-oxy-4-biphenoxy group and a4-[1-(4-oxyphenyl)-1-methylethyl]phenoxy group.

30. A crosslinkable-group-containing polyimide according to any one of claims 1-18, wherein there is a temperature T [°C] which simultaneously satisfy the following numerical formulas [2] and [3]:



where

MV5(T) :   melt viscosity [Pa·sec] of said polyimide as measured under a desired constant shearing stress in a range of from 0.1 to 1 [MPa] after causing said polyimide to melt by holding said polyimide at a temperature T [°C] for 5 minutes; and

MV30(T) :   melt viscosity [Pa·sec] of said polyimide as measured under said desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing said polyimide to melt by holding said polyimide at the temperature T [°C] for 30 minutes.

31. A crosslinkable-group-containing polyimide according to any one of claims 1-18, wherein there is a temperature T [°C] which simultaneously satisfy the following numerical formulas [2], [3] and [4]:





where

MV5(T) :   melt viscosity [Pa·sec] of said polyimide as measured under a desired constant shearing stress in a range of from 0.1 to 1 [MPa] after causing said polyimide to melt by holding said polyimide at a temperature T [°C] for 5 minutes;

MV5 (T+20) :   melt viscosity [Pa·sec] of said polyimide as measured under said desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing said polyimide to melt by holding said polyimide at a temperature T+20 [°C] for 5 minutes;

MV30(T):   melt viscosity [Pa·sec] of said polyimide as measured under said desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing said polyimide to melt by holding said polyimide at the temperature T [°C] for 30 minutes; and

MV30(T+20):   melt viscosity [Pa·sec] of said polyimide as measured under said desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing said polyimide to melt by holding said polyimide at a temperature T+20 [°C] for 30 minutes.

32. A crosslinkable-group-containing polyimide according to any one of claims 1-18, which simultaneously satisfies the following numerical formulas [5] and [6] :



where

MV5(360):   melt viscosity [Pa·sec] of said polyimide as measured under a desired constant shearing stress in a range of from 0.1 to 1 [MPa] after causing said polyimide to melt by holding said polyimide at 360 [°C] for 5 minutes; and

MV30(360) :   melt viscosity [Pa·sec] of said polyimide as measured under said desired constant shearing stress in the range of from 0.1 to 1 [MPa] after causing said polyimide to melt by holding said polyimide at 360 [°C] for 30 minutes.

33. A crosslinkable-group-containing polyimide according to any one of claims 1-18, wherein a time t (min) which satisfies the numerical formula [7] lasts 10 minutes or longer:

where

G' (t) :   storage modulus of said polyimide as measured at 360°C and 1 Hz after an elapse of said time t (min); and

G" (t) :   loss modulus of said polyimide as measured at 360°C and 1 Hz after an elapse of said time t (min).

34. A crosslinked polyimide obtained by heat-treating a crosslinkable-group-containing polyimide according to any one of claims 1-18 and claims 30-33.

35. A solution or suspension comprising a crosslinkable-group-containing polyimide according to any one of claims 1-18 and claims 30-33.